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SYMMETRICAL  DTISOPROPYL-HYDRAZINE 
AND  RELATED  COMPOUNDS 


BY 

HARRY  LOUIS  LOCHTE 


B.  A.,  University  of  Texas,  1918 


THESIS 

SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  REQUIREMENTS 
FOR  THE  DEGREE  OF  DOCTOR  OF  PHILOSOPHY  IN 
CHEMISTRY  IN  THE  GRADUATE  SCHOOL  OF 
THE  UNIVERSITY  OF  ILLINOIS,  1922 


URBANA,  ILLINOIS 


V 

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UNIVERSITY  OF  ILLINOIS 


THE  GRADUATE  SCHOOL 


May  23 192-Z  - 


I HEREBY  RECOMMEND  THAI'  THE  THESIS  PREPARED  UNDER  MY 

SUPERVI SION  BY HAMY_ I^OU IS  LOCHTE  ■ 

ENTITLED _S:UL£ET.RI CAL  DI-ISOPHQPYL-IIYDPAaTRS  AND  RELATED 

COi^OlTJDS 

BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 

THE  DEGREE  OF Doctor  of  Philo sop)i;^>- 



In  Charge  of  Thesis 

; ^ uCAAA^ 

^ Head  of  I^Iepartment 

r 

Recommendation  concurred  in* 


pA  ^ ^ ] i*‘  4^ 


Committee 

on 

Final  Examination* 


Required  for  doctor’s  degree  but  not  for  master’s 


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The  writer  wisxies  to  express  his  appreciation  of  the 
inspiration  and  the  helpiul  suggestions  of  Professor  W.A.l^ioyes 
under  whose  direction  tiiis  investigation  was  carried  out, 

he  also  wishes  to  express  iiis  gratitude  for  the  never- 
failing  help  of  Professor  J.R, Bailey,  of  the  University  of  Texas, 
at  whose  suggestion  Luis  invest/igaoion  was  begun  and  under  whose 
direction  tue  first  part  of  tiie  work  was  carrieu  out. 


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I IwiHUDUUTIUN 

When  reports  on  Lhe  success  of  catalytic  metnoas  of  re- 
duction, using  platinum  or  paliauium  as  catalysts  and  nyarogen  gas 
as  reducing  agent,  showed  more  and  more  cases  in  wnich  complexes 
could  be  reuuced  tiiat  had  not  been  reducible  before,  professor 
Bailey,  of  txAe  University  of  Texas,  suggesieu  tiie  reduction  of 

cHj 

dimethylketazine,-':^c.-'^-'^  - , oy  uas  me  chod.  Although  all 

old  methoas  haa  iailea,  catalytic  reduction  proved  comparatively 
easy.  The  problem  was  then  transferred  to  the  University  of 
Illinois  where  the  work  was  continued  under  the  direction  of 
Professor  W.A.iMoyes. 

The  preparation  and  study  of  vai’ious  derivatives  of  the 

hydruzo  compound  (symmetrical  diisopropylxxydrazine ) was  next 

undertaxen  because  neretofore  alipnatic  hyarazines  nave  been  too 

difficult  to  prepare  to  study  tnem  in  detail.  Tne  mono-nitroso 

uerivative  of  symmetrical  diisopropyl-iiyurazine  was  prepared  and 

proved  very  interesting  because,  conorary  to  expectations,  it 

of 

forms  a sodium  salt.  The  quesLion  of  the  strucLure^ni troso-hydra- 

A 

zines  ana  tiieir  metal  salts  is  tnus  raised  again. 

Both  tiie  azo  and  tiie  hyurazone  compound  corresponding  to 
the  symmetrical  hydrazine  were  prepared  as  the  first  case  of  iso- 
lation of  both  tautomers  of  purely  alipiiatic  compounds  of  this 
type. 

Primary  isopropyl-hyarazine  was  prepared  by  reduction  of 
a mixture  of  equimolecular  amounus  of  acetone,  hydrazine-hyarate  , 
and  hyurociiloric  acid^  by  the  acid  iiyurolysis  of  acetone- isopropyl- 


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iiyd.razine7  and  by  tne  acid  nydrolysis  of  2 , 2 * -azobispropane . 

II  THEOKETICAL 

Since  the  discovery  of  nydrazine  oy  Gurtius,^  and  tiie 

2 

development  of  a metxiod^by  Kascnig  , by  means  oi  which  hydrazine 
and  its  salts  may  now  readily  be  made  at  reasonable  cost,  the 
interest  in  tne  many  types  of  nydrazines  ana  tneir  derivatives 
has  grown  constantly, 

Emil  I'ischer'^  made  the  first  derivative  of  hydrazine  when 

he  prepared  and  studied,  in  great  detail,  the  poisonous  base, 

di 

piienyl-hydrazine , made;  by  him  througix  the  reduction  of^azo- 

A 

benzene,  Metiiods  of  preparing  aromatic  hyarazines  are  quite 
numerous  and  these  compounds  have  long  been  tnoroughiy  stuaiea, 

for  tiie  alipnatic  hyarazines,  nowever,  few  methoas  of  pre- 
paration are  known  and  almost  without  exception  the  yields  obtained 
by  methods  known  before  tne  discovery  of  the  method  used  in  this 
investigation,  are  poor, 

I'or  the  preparation  of  the  unsymme trical  secondary  hydra^-^ 

4 

zines  Emil  riscner  worked  out  a method  tnat  gives  fair  yields.  He 
prepared  the  nitroso  compounds  of  secondary  amines  and  reduced 
these  with  zinc  dust  and  acetic  acid.  Another  metnoa  or  preparing 
unsymmetrioal  hyarazines  was  developed  oy  tne  same  chemist  and 
may  De  expressed  by  the  equatioii^, 

KBr  — ^ C .H^(h)iM-NH9,HBr  , Txiis  method  is  usually 

O -j  2 DO 

used  only  to  prepare  mixed  disubstituted  hydrazines. 


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For  tne  preparation  of  simple  primary  ujurazines,  Fiscner 

also  developed  a metxioa.  It  may  be  iilus orated  by; 

Re  auction  &: 


KWH 


Ri\H 


:u=o 


ni\iO 


Kivn 


Alkali  RiMHp  + 
K- w -w  0 Acid  Kw  Him  H o 


^CrO 


KRH  RN  NO  RNnNHp 

T b Alkali  or^  --..-i  ^ 


HgN 


IN  Hr 


NH. 


^2  acid  — 'o 

For  symmetrical  disubs LituLed  hyarazines  the  use  of  alKyl 

halides  (usually  the  bromide)  yields  a mixture  of  symmetrical  and 

unsymmetrical  hyarazines  wnich  may  usually  be  separated  with  more 

or  less  difficulty.  A more  serious  difficulty  exists  through  tne 

fact  oiiat  it  is  almost  impossible  to  prevent  tiie  formation  of  the 

7 

quarternary  ammonium  compounds,  i'he  safer  and  more  economical 

method  of  preparing  these  nyarazines  oy  alxylation  protects  tne 

second  H on  each  nitrogen  atom  uy  acetylation  or  formylation.  Then 

the  alkyl  groups  must  go  to  uifferent  nitrogens  and  thus  produce  tiie 

symmetrical  seconuary  xiyurazines.  This  is  the  metnOd  tuat  was  used 

8 

with  some  success  oy  Harries  ana  coworxers  . Tney  were  aole  to  pre- 
pare the  symmetrical  dimethyl  ana  dietnyl  nydrazines  by; 

ChO-N-n-ChO  » GhO-(R^iM-iM(R)-ChU > KNH“i\iHR 

Vb 

The  yield  was  low  tiiough  and  tney  were  aole  to  do  little  more 

9 

than  isolate  tne  aoove  compounus.  Htolle  also  did  much  work  on 
this  method  of  preparing  aliphatic  nyarazines  and  he  and  coworkers 
were  able  to  aajust  conditions  so  as  to  obtain  a certain,  if 

9 

small,  yield  of  symmetrical  hyarazines.  Buscn  was  aole  to  prepare 
under  these  conuitions,  small  quantities  of  primary  isobutyl- 
hyarazine  and  smaller  yielus  of  tne  corresponaing  symmetrical 
and  unsymmetrical  seconuary  compounus. 


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Buscn  and  SLoile  also  used  a uixferent  metiiou  for  the 
preparation  or  symmetrical  uisubsti Luoed  xi^arazines . Ixieir  metiiod 
may  be  expressed  by; 


I\iH2bK2 


,K^O 


+• 


OK 


OK 


.OK 


i\iK2KHK  •+  KHSO^'+  ^20 


ana 


kKK“'KH2  bO^^,, — ^KKJM“1NHK-K  KiibO^ 

jiven  uere  tue  yield  is  poor  anu  uncertain  since  sometimes 
symmetrical  and  sometimes  unsymmetrical  hyurazines  are  formed  as 


the  main  yield. 


Kischner  developed  a metnod  that  was  originally  used  for 
the  preparation  of  primary  hyurazines  accoruing  to  the  reactions; 

RK  ’ CH-NH2*b  -br2  -h  KuH  ^ KR ' GH-KKBr-f.  xv^r  H2O 

KK  ‘ GH-Khxjr  KhK-GHKR‘ > KR ' GH-im-iMrCRK  ‘ 2H5r 

Tii.e  hyarazone  tnus  lormeu  is  buen  uydroly zea , ii  uiie  primary 
hyurazine  is  to  be  formed.  Catalytic  reuuction  anouiu  easily  re- 
duce the  same  rijurazone  to  one  symmetrical  seconuary  iiyurazine. 

finally,  Gurtius  anu.  student s"^^  found  tiiat  hyurazine 
hydraxe  and  aluenjaes  or  xe tones  condense  to  lorm  simple  hydra- 
zones; 


KK ’ CrO -hK;j;U“hH2  .HoO — >KK’C-W“wH2  2 H2O. 


Tnese  Gompounus  are  very  unstaule  ana  are  eitner  hyarolyzeu  to 
the  original  suustances  or  they  react  with  anotxxer  mol  of 
alaeiiyde  or  keLone  to  produce  azines; 

Rk’CZI\i-NH2+  0^5=CKR‘ — > KR'GsK-H=CRR'  -v  H2O 


Althougn  Gurtius  auid  others  were  aole  oo  reduce  benzalazine  and 
some  OLner  aromatic  azines,  Lhey  found  txiai.  tne  aliphai-ic  azines 
are  perfectly  staole  towards  alKaline  reducing  agents  v/nile  no 


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reducing  agents  couia  be  usea  in  un  aciu  meaium  because  the  azines 
are  reaaily  h^droi jzed  by  acias. 

13 

Gurtius  as  well  as  Vvonl  and  uesterlin  made  primary  benzyl- 
hydrazine  by  paroial  reaucLion  o!  benzalazine  and  hyurolysis  oi  the 
hyarazone  lormed, 

Dimetuyl-ketazine ,on  reduction, yielas  symmetrical  diisopro- 
pyl-hycirazine  and  tnis  , in  turn,  yields  azobispropane  and  other 
inLeresting  compounds.  Always  xiopaogLhat  tne  reduction  could  be 
effected  in  som.e  way,  a number  of  chemists  have  recorded  failures 
in  attempts  to  reauce  this  compound.  Curtius^"^  trieu  to  reduce  the 
ketazine  by  alKaline  reuucing  agents,  out  found  it  peneculy  stable 
Lowarus  L-iiese.  ixiieie  could  noL  reauce  ii  by  an  eiectrolyLic 
method  with  which  he  had  just  reduced  benzalazine  to  tiie  corres- 

1 K 

ponaing  hyurazo  compound.  He  also  aLtempiea  to  prepare  the 
symmetrical  hydrazine  ne  iiad  nopea  to  obtain  by  reduction  of 
aime thyl-ketazine  through  the  elimination  of  2 molecules  of 
carbon  dioxide  from  hydrazo-isobuty ric-acid, . 

^ 'Go  dH  y G O dn 

V/ieland  reports  tnat  tne  alipnatic  alGazines  are  'noL  reducible. 

18 

kailhe  was  able  to  affect  the  reduction,  but  the  product  obtained 
consisied  of  a mixiure  of  mono  and  di  isopropyl-aonine  instead  of 
the  hydrazo  compound  he  sougnt  to  obiain. 

In  the  course  of  the  present  investigation  many  unsuccess- 
ful attempts  were  made  to  reduce  dime tnyl-ketazine  by  various 
common  reaucing  agents,  acid,  neutral,  and  alkaline.  Althougii  a 
few,  such  as  sodium  amalgam(4/j) , sodium  in  alconol,  and  aluminium 
amalgam  gave  small  amounts  of  reduction  proaucts  tixat  were  basic 


t 


- 6 - 

none  oi  Liiem  were  idenLical  wIlu  uhe  symmeLricai  h^arazine  uhau 

was  oeing  prepared,  in  the  meantime,  the  catalytic  method 

described  hereailer.  Otiier  reducing  agenos  sucn  as  zinc  in  aciu 

solution,  potassium  hydroxide  and  aluminium,  iron  witn  hydrochloric 

aciu  or  aceLic  acid,  and  reauction  oy  stannous  ciiioride;  all  failed 

to  give  any  nooiceaoie  reauCLion  oi  the  ketazine. 

In  tesLing  for  a possible  basic  product  formed  during  one 

of  tue  unsuccessful  attempts  descriueu  above,  white  needles  of 

a dii'ferenL  compound  separax-ed  out  on  aading  benzoyl  ciiioride  in 

Lxie  hope  01  obtaining  a benzoyl  compound  ox  the  reduction  product. 

Ine  melting  point,  appearance,  and  analyses  indicate  that  tiie 

product  formed  is  the  benzoyl  derivative  of  5-methyl-5-dim.ethyl- 

H -C C — GH^ 

pyrazoline,  " 


lb 


GH . 

I'i 

i'i— OQ— G ' il 


Gurtius  and  cowSrxers,  i^ranke,  and  j?rey  and  Hoiiman 


found  that  ketazines,  if  they  have  a metnyl  group  next  to  tiie  G=i\i 

complex,  readily  rearrange,  when  under  the  influence  of  dilute 

acids  to  form  pyrazolines.  Dimetnyl-ketazine , tiius  treated, 

rearranges  to  form  o-metuyl-b-uimetnyl-pjrazoiirf©.  Hven  maleic 

acid  is  aole  to  cause  tuis  rearrangement  in  tne  case  of  tnis 

19 

ketazine,  Gur  tius  anu  Wirsing  i ounu  tuat  tiie  same  pyrazoline 
is  also  formed  wnen  mesityl  oxide  is  treateu  witn  hyurazine.They 
prepareu  a benzoyl  derivative  of  the  compound  tnus  prepared. The 
properties  given  by  tnem  agree  witn  those  found  in  the  present 
investigation.  The  small  acid  concentration  due  to  liydrolysis  and 
to  formation  of  the  derivative  is  then  sufiicient  to  produce  tiiis 
rearrangement  of  dimetxiyl-xetazine , 


..  icoLJiieui  o*...*  nviJ  otu. 

'''•^r.'jO.t  r;i j'\,ir.1i3C  '• '■2t  ■ , t.-riiJ  n;>r’m  r>nJ'  ri  «i;’3 qo*\q  sfo 


r.  ■ tx  OP.  leriJC.  .TeJiAsiba  ;5if o«ei.  n' 


» r.i;  .^ivs  n,,n  ^ . i uir,  k.na  ncxrxs.ox.  cq  ,f.C'Iux'XC 


«./' 


f 


' ‘ ■ il/,  '■  tI  O'  i.x.lt'  aij  '.U'X'f'l  t ''*»  ^vicx  oJjiCXJ  IC  JJII;  ^ 


♦ X\fc‘wCA  Vj*^  OXwt^^OiilC'4^.  XV.  C ^ 

i 

.,  -rri'i  T'.'-*?.--  ac  i ‘Viq  U xcv.  -s  '^c.  i.  y^'i 

' ■f’  i 

’’i  C h'.  ) ' ?•'*'  ffJ'j-i  t I !*■  V ' ''X  L-/*i  i ' ' X t<  £^r  («>' >'j/i  s>>M>  <3  XS/t-a»oOt>  4 > c«  i 'JJ  X . 0 X 

; o". .t"*" ‘r.w  .'.vf^  r"- o'  /i<v  x t.i a.c:.  o i ■ryi> j. i j.L 

'■' V.'. . r . :- V fj;  > c ^;'''  .w-  ojirt.  x ^iiAX 'xca:  '-lc  x.|t.  < 

.'k  -i  rr’ ' J^A/v.  t-’x  . ^e. X t'x- - . uj:h':3;x..;  >i 


\ ■’  * ^ • o c jL  k'lXi/  ^ J rti i»l  o I j X)tC’ i(j  z •i I fjt.j \t'^ 

' .j\ 


- , ATti  LC. 
.'T.-> 


/'  pi*-.-  . 

./j.  r.n  ii 

flj*  t -*«*')  . i o i .3  l^ 


^ ' .1  ^ -J  ,'3r;j‘  if  -'jio 

I. 

eoV;/!!'  tc  0 Ir*  ^ ’-'-jjv.f  v ) y>3ri  i ,.:•:  iqu 

/ 

f t.)  f , ii<  ciV'ito  A - > "f  j ■ <'i:iva  ivjrfiJj  «t  li)  i u-f  ^*/X 

.i  ~ rr-rr  *cr  ' .(05  **•)  ^ ••  - .-,  va/-3- f ry  r-^  *;i\Oi  OJ 

Uj  .^  io  * •• } i :'•*•  r.- h/i-a  o:  *>[.-.  cX  »j2 

t.ii'  -(T>^2  '’rfJ  ;irr.  ^.•7.  c i , t\i^ 

. 3;-ii  r A'j.‘ ,;.ff  rJ.tr  Jra.-Kcrf’  j i i'i  ihoi/i  n >fl-*  x»«t:  ) . i ubifi 

' . -*’r  ■ . 6«;r  + ftp.  J ; ‘^i  v,'.'iw«  *•  oe  ogj 

J 't.  ; 0 Mr.-'  -1  "IX'^  “?cr  .f  lK*.t?^  **«  '"niU  > ci  .-i.lJTr.qO 

C'''.'i  i Ir,  'i.*^4;  c«^  *L,t-  'TiJ.'jT  rrr  u .co  IIxtu  f^T  . rx 2.i/?ni  i80V  J 

■ * ‘ •*  ■ • * r -"i  ■•  t ^ ? r * T ♦ j > ...  * i,  > 


i j 

. - r »/  j j>  't('  xr.ci;?  .tt/  i 


-7- 


2(1 

Zlehl  attempted  the  cataijLio  n^urogenation  (SkiLa 
methou)  of  a series  of  compounas  of  niLrogen.  Among  these  were; 

iminotriazomeLxiane  — • and  aiazoaminobenzene.  He  was 

HH2 

not  able  10  reduce  any  of  tiie  wro  or  h=iM  complexes  shown. 

In  experiments  with  isocyanides  ne  was  aule  uo  reduce  the  eom- 

1 

pounus  to  trie  uorresponuing  methji-amine  aerivatives  only  in  case 
the  isocyaniaes  were  so  stable  Liiat  no  formic  acid  was  formed.  In 
the  case  of  iminotriazomethane  iie  could  observe  no  aosorbtion 
of  hydrogen,  although  he  found  that  campnor  oxime  could  readily 
be  reduced  to  bornyi-  amine, 

Quite  recently,  Staudinger,  using  a catalytic  raetnod  of  re- 
ducLion,  reduced  diazo  compounds  ana  obtained  hydrazones,  but  did 
not  reduce  these  lo  Lhe  nyurazine.  In  view  of  tne  lact  that,  as 
will  ce  Siiown  later,  saliiication  01  oixe  base  formed  during  the 
reducLion  is  essential  to  success  in  cue  reaucLion  of  most  such 
compounas,  it  is  possiule  cxiciL  ne,  too,  could  uave  reauced  the 
G;N  complex  readily  ii  he  nad  run  txxe  last  step  of  'lxiIs  reauccion 
in  an  acid  soluLion, 

ine  worx  on  Lnis  problem  snows  tnat  the  re auction  of  di- 
metnyl  ketazine,  and  prouably  oi  otxxer  azines,  can  be  carried  out 
with  very  satisiactory  yielus  tnrough  the  use  of  catalytic 
methods  of  reduction  employing  finely  divided  platinum  or  palladium 
eitner  as  the  platinum  or  palladium  black,  or  in  form  01  the  pro- 
tected coiloia  of  eiuxer  metal, 

GataiyLic  reauction  by  cue  use  oi  Lhese  me  cals  ua.s  been 
xnown  lor  over  ixaif  a cencury,  buL  tne  possiuilities  of  these 
meLhoas  were  noc  recognizea  until  afcer  oixe  year  lyOO  and  inten- 


I ' 

l! 


1 


il 


t 


- * t 


^ V J Si  ^ Mi  '**"  ^ , X - * 


' /.  * 


• tj $ i i.*»’U  \* 


..'  * ■ *'  ' * 
. i C ,^.V  .*v  i *. 
M .'  i <J  .'.A  .v'Xl 


n-  '•^»»4ii4  ; M m f,  — • ,'*^’  w*^y* 

W T tj'’" 

^ ,^-/|V4.  5*.«  i > - t -Hf 

* '.  r .'  \[,  j V *.  'i  •»  St  .*  . - M «.  1 t <•  _ ' M .« 

T. 

. f " i -.r  r ■ j.  ■ . V ...  A '' ' 


'is.-  J 1*4  I 3 . » - sJ 


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j.iJ'ti*:''  V x.s.  ; ' 'i.j.A.C  ‘5 \ (.-•..  M V >i4w  4 


. . ..  , rr  rx  . n 

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~ ,1  • 5'..  04  fj? ''s  ‘ 


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'>  fV.  jDil.  4/4*."..  4..1.J  X.)  fC4./  .ix  4 SljS.A'to  s.  -..',4.  'mV 


X 


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C>i3'  ..  hi  4 ;yn/i  . .*vi  .. 

f 


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j 1 l.'i ; K.  I'.  -t  A 5 * *.  i -.14-;  x.  » •- 

.5  . I „ .1  • 4 ..  ~ i.J  V 4 - -4  V i.iAaV  A i M ^ ..... 

j i ..  J .'  1 3 J J J I ])  . > 5 V t4  1 < / i .r.  i 1 • M .».,.■  4.  V _ J < ..  i> 


‘♦_ 


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i«L.^  j.:_*.  M-  -:9  . 


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XX. I ‘ *]  iA-  C4^  J i ^0.7*4  .'tV  Ji'A#  M444  1.-*  4.  4.- 


i - A J 4,  _ . .VV 


.if"  •■-i  , 


L 


V l 3 1 A V J r .t  V A ..  i j rt 

- - 4 u:  i»Mn  }<.i*~.x  - ' . . 


L^w  i|vl  «# 


JT-!W‘  • 


<-1-  - *•  - V . _ .-'.s.  JK  . .-.  . .,J  a;i 

-.a-r  -^-aa 


.11 


- 8 - 

sive  investigation  or  txiese  metnoas  was  not  oegun  until  alter  1907, 

oince  tnen  turee  main  metnoas  nave  oeen  worKed  out;  (1)  tne 

22 

Willstatter  metnou,  using  platimim  olack  prepared  according  to  the 

metnou  oi  Loew^  bhe  paal  methoa  ^*^employing  colloiaai  platinum  or 

palladium  protected  the  soaium  salt  ol  eitner  protaluinic  acid 

or  lysaibinic  acid,  availaule  only  for  reduction  in  alkaline  or 

, . 25 

neutral  solutions j ( b)  the  3kioa  metnou  uses  gum  arabic  instead  of 

the  sodium  salt  of  <a.n  acid  as  a protective  colloid.  In  the  case  of 

the  3kita  metnOu  tne  protective  colloid  is  effective  in  either 

acid,  neutral,  or  alKaline  ciOliition  . Ao  ulie  end  ox  the  run  the 

colloiu  is  removed  by  precipitation  with  acetone  and  filtering, 

Skita  also  originatea  tne  principle  ox  inoculation  in  catalytic 
25a 

reduction  ; a small  amount  of  piatinic  or  palladous  chloride  is 
reduced  separately,  oy  partial  reduction  in  iiot  aliialine  solution 
by  means  of  a few  cr;^stals  of  hydrazine  njurocnioride  in  case  oi 
the  platinum,  and  by  passing  nydrogen  gas  tiirough  the  hot  palladous 
chloride  solution,  in  case  of  tne  palladium,  A few  cubic  centimeters 
of  this  stock  solution  is  then  employed  as  a ’'seeding'*  colloid 
that  aids  in  the  reduction  of  tne  main  mass  of  platinum,  which, in 
turn,  catalyzes  the  reduction  of  tne  substance  in  question. 

As  it  appearsG  to  be  the  most  convenient  and  the  most  pro- 
mising for  tne  reduction  of  tne  azines,  3K.ita's  method  was  selected 
for  worh  at  the  University  oi  Te^as,  It  was  successful  from  the 
start  althougix  early  runs  on  ketazine,  water,  ana  colloidal  plat- 
inum protected  oy  a small  amount  oi  gum  arabic,  required  a large 
amount  of  catalyst.  Of  xen  as  much  as  100  c.c.  of  chloroplatinic 


41 V- 


Oi;. 


. J rC-Tv 


(’••../  ;v 


I I 


'-.iU,  it.)  : •' 


.'■/T  ■■■ 

, i 


,.  v,;i 


\ 


»•  1 ^ - 1 X %^xJl 
,:.U’  t\*P 


i 


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; s'J 


'ir'^ 


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VJ:  L 


•jjrv 

’•>  ■! 


f-tn.  I'.'X  1 4i> 


' V* " II  mm  ^ V-  ^ 


r*''< 


VC^ 


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..  , , ic.  '■■•/Ij 


c Jlze  tiuJi  . I 


; 


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.3*  ne|^t^ 


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i 


"i"'  ■ • ' !'.  ^ *»!■< 

<TC.tv»  (.  _ I 


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;.*•,«  -ciU  ■ 'xV“:nc  : . 


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:.c  _ .A  ; , 

- fi'  , t;  J.v 


'I 

y iKJt  X.{.« • 


liA  Xii., 


- y - 

acia  iiaa  to  oe  emplo^ea  in  tne  reduction  of  100  c.c,  of  dimetnyl- 
Ketazine.  jiven  witn  tne  large  amount  of  catalyst  the  yiela  was 
only  about  eighty  per  cent  and  several  days  were  required  for 
completion  of  tue  reduction.  In  attempting  to  improve  the  yield  or 
at  least  curtail  tne  amount  of  platinum,  it  was  found  that  neutral- 
ization of  the  base  formed  as  the  reduction  proceeds  immensely 
accelerates  the  reacLion  and  maKes  it  possible  to  complete  the  re- 
uucLion  in  a single  aay  witii  less  than  one  lourch  of  the  amount  of 
platinum  lormerly  used,  liie  ex^ra  cnioroplaxinic  acia  used  in  the 
initial  experiments  procaDly  owed  its  main  effect  to  tiie  uydrochlor* 
ic  acid  liberated  on  reduction  oi  the  acid,  ratner  chan  to  the 

additional  amount  of  colloidal  platinum  tnis  aaded  to  the  re- 

2 5e 

auction  mixture  • oince  txxen  an  article  by  oxita  has  appeared 
in  Wiiich  he  makes  tne  saijie  ooservation  on  tne  effect  of  hydrochlor- 
ic acid  in  a similar  case.  Experience  in  Inis  research  indicates 
ciiat  salification  is  always  advantageous  when  a case  is  formed 
in  catalytic  reduction. 

During  the  first  few  neutralizea  runs  txie  necessary 
nyarochloric  acid  was  added  at  different  times  during  tne  run  be- 
cause it  was  I eared  tnat  hyarolysis  of  the  ketazine  by  a >greater 
concentration  of  acid  woula  diminish  the  yielas  obtained.  Later  it 
was  iound  that,  in  spite  of  tixe  claims  of  Curtius  and  others  that 
ketazine  is  immeaiateiy  nydroiyzed  oy  mineral  acids  ,tne 
addition  of  tixe  theoretical  amount  oi  acia  ac  tne  ueginning  of  the 
run  in  no  way  diminishes  tiie  yielu  of  yu-yo/o  of  tixeoreticai  (based 
on  the  amount  of  xecazine  usea)  wnicn  is  obtainea  wnen  the 


- 10  - 

neuLrallzation  is  aone  in  steps. 

Since  tiiis  unexpected  result  seems  to  inaicate  that  dimethyl- 
ketazine  is  not  hy aroiyzea  to  an  appreciable  extent  by  the  diluLe 
mineral  acid  under  the  conuitions  oi  tiie  experimen’^,  it  appeared 
iikelj'  that  reduction  ox  a mixture  of  one  mol  of  nydrazine  nyarate, 
one  mol  of  nydrocnioric  acid,  and  two  mods  of  acetone  woulu  give 
the  same  results  while,  at  tne  same  time  ooviating  Lxxe  isolation, 
witn  ratner  unsatisfactory  yields,  of  the  xetazine.  In  tnree  runs, 
where  ih  each  case,  25  g.  of  hydrazine  hydrate  in  250  c.c,  of  water 
were  employed,  tne  reduction  required  5-4  iiours  and  the  yields  were 
7s, 80, and  74  g.  of  tne  nyurochloride  oi  symmetrical  diisopropyl- 
nydrazine,  Altnough  only  once  recrystallized  and  oiierefore  not 
pure,  samples  Oi  txiis  salt  meiteu  ac,  19  7-8'^,  had  a chlorine  content 
of  25.8  % (by  titration  witn  silver  nitrate  uy  MOhr’s  method),  and 
5 iodine  titrations  gave  an  average  purity  of  95.5/0  (2  atoms  o± 
iodine  to  1 mol  of  the  ixydrazine)  tuus  indicating  a yield  that  is 
practically  quantitative. 

The  hydrazo  compound  formed  in  tne  reduction  of  dimethyl 
ketazine  is  similar,  in  the  main,  to  otner  symmetrical  hydrazines. 
AS  is  often  tne  case  with  aliphatic  nyurazines,  it  is  difficult  to 
obtain  the  base  completely  anuj,urous.  Like  symmetrical  dili€n3.*ji  , and 

in  contrast  to  symmetrical  dimethyl  and  diisobutyl  hydrazines 

27  , , . , ^ 

wnich  form  uoch  neutral  anu  c».cid  salts  , tne  uase  uerived  xrom 
dimethyl  ketazine,  in  all  reactions  so  far  observed,  is  monobasic. 
The  behavior  towards  mild  oxidizing  agenus  iso  different  from 
tnat  of  the  corresponding  dimethyl  ana  uietnyl  compounds. 


i ' IP- ‘ I . J ; ' V . 'v  *.  t --.  . ' 

.1 

"i  'iC-i-  ^ j . ., 'J  '. .:  j Li-'.-  ■..' .!?■ 

*< 

J /)  ; (.W  AC  ■ >ij  ) ( . ,i  ' 

y . 

iV  I '^nfl-  *U’ibCl  •>!.  ' 


/ V 

- i i 


11 


iiie  preparauion  of  Lhe  usual  simple  SialLs  and  aerivaLives 


of  nyurazines  ofiers  no  uiifiouiLies  in  tue  case  ol  Lne  symmelrical 
hydrazine,  except  in  the  case  of  une  oenzoyl  derivative  which  does 
not  appear  in  satisfactory  crystalline  form  uut  as  a smear  which 
could  not  ce  made  to  crystallize.  This  cenavior  of  the  benzoyl 
aerivative  is  ratiier  common,  however,  in  Lne  case  of  uydrazo 
compounds. 


most  easily  preparea  derivatives  of  symmetrical  diisopropyl-hyura- 

zine,  txie  oxal  .abe  is  orouulesome  cecause,  as  in  a number  of  ocher 

29 

oxal  .ates  of  ayarazo  compounus,  it  seems  to  form  a mixture  of  salts. 
In  tne  case  of  tne  case  unuer  consiueration  the  aonormal  results 
ODtained  on  analyses  seem  to  iiave  ueen  due  to  tae  fact  caat  the 
salt  consisted  ox  a mixture,  possiDlj  ox  tae  simple  ana  tae  douule 
oxalJates.  After  6-8  recrystallizations  from  alconol  tae  product 
obtained  has  a melting  point  of  200°  and  analyses  show  tiiat  tae 
compound  has  the  formula;  ^ 


Waen  a mono-alxyl  hyurazine  is  createu  with  nitrous  acid,  the 


imide  hydrogen  atom  is  sucstituted  as  is  seen  from  the  fact  that 
these  nitroso-hyurazines  still  condense  with  alueayaes.  In  the 
presence  oi  c^myl  nitrite  and  alkali  cxie  nitroso  mono-alxyl  ayara- 


form  an  isoazo cate,K— NshOna, 

xae  raono-arjl-ayarazines  here,  as  in  most  ocaer  respeccs  do 
not  uiffer  greatly  xrom  cae  alipnatic  ones.  In  tae  case  of  paenyl- 


Altaouga  it  is  one  of  cue  most  beauciful  ana  one  of  tiie 


zines  can  ox  ten  be  made  to  react  again  with  nitrous  acia 


to 


I 

f 

I 


I 


12 


hydrazine  and  its  suustilution  produces  and  in  tiie  case  or  benz^l- 
iijQrazine,  sodium  sal  os  are  lormed  from  oxie  nirroso  compounds, 
mis  meral  may  tixen  readily  ue  replacea  vj  alkyls  v/nen  alkyl  naliue;; 
are  per.iiotea  oo  react  witn  tixe  salts*  Tne  structure  of  onese 
sodium  salts  has  not  jet  ceen  deiiniteiy  established,  probauly 
two  or  more  tautomeric  forms  exist  in  equilibrium,  somewhat  as  in 
the  case  of  acetoacetic  ester  or  in  trie  oximes. 

In  the  case  ni trosophenyl^hjdrazine  a sodium  salt  is  formed 
wnen  the  base  is  allowea  to  react  witxi  sodium  methylate  in  the  ab- 
sence of  water,  ihe  sodium  replaces  an  H from  phenylhydrazine , but 
tixe  exact  hyarogen  atom  involved  xias  not  yet  been  uefinitely  de- 
termined, Tne  salt  could  ue  formed  by  any  one  of  the  x-ollowing 
reacLions  j 

1)  GfeKaH— NHgt-  i<aUCH_3->  Cy-i^-W  GK5OH 

hO 

2)  Cmui'isNh  -I-  naUUH^ — ^ -J—  CH5OH  1 

imUH  wQWa 

5)  CgH-NH-WrwUH+kaOGH3 — > C^H5-wh-i'j=N0Wa4bn30h 

4)  K — ri4kaOCH. — v G^fHr. Ciir^OH  ' 

IMOH  ^ ^ iMQNa 

The  Lnira  form  is  maue  extremely  unlikely  because  of  the  similarity 
of  ni trosophenyl-hyurazine  to  alkyl  nitrosohydrazines,  especially 
nitrosobenzyl'-xjLjurazine , in  wnicu  tixe  presence  of  an  amino  group 
is  established  txxrough  the  condensation  oi  the  ni troso-nydrazine 
with  aldehydesi?^  Moreover,  careful  oxidation  of  the  nitroso  com- 
pound witn  cupric  sales  leaas  to  a uyuroxylamine  uerivacive.  Tiiis 

compound  could  naraly  lorm  unless  tne  siruciure  were  tnai  given  in 

32 

1)  unaer  tne  condieions  oi  the  experiment  , Finally,  the 
reduction  of  the  uenzoyl  uerivative  of  niirosopnenyl-hydrazine 
leads  to,*^^  C.  C». . 

V.  H H 


i f . ■ ‘ 

‘ .Vlf  , 

a*  f i |'.‘>|J|''  - 

> . f ■■  . 


o^' 


/» 

II 


li 


N>> 


Vi 


• ’ I 

' I ^ . •;'■!  ( 

;<  , r . 

.,x!'  ,.  '.  ' y \ ' i 


> 

^ e-i.J  nr  /.  I 

--I 

• . •■'  . ,j 


tr  *>  ’ 


ur 


r . . 

- I 

* ! 

' . ‘Tjlt’.  -'»v.  '■  '■•  . j.  • ^;  ,'x^ 

ji  , ■ * t‘’-»  ■ »•  . "ill  fv-  **' 

;i 

ji  I;.  . f #■'  A J* 


t 


1,1, 


^ rj 


I c oTfai  if 
T 


Lr* 


lo 


5 b 

Fischer  in  nis  original  investigation  oi  nitroso-pnenj 1- 
iij'urazine,  consiuerea  tnat  it  was  a normal  nitroso  compouna  oe- 
cause;^l)  reduction  leads  to  aniline  indicating  that  txie  nitroso 
group  is  not  attacheu  to  tne  benzene  ring,  ana  (2)  in  amines  nitroso 
compounds  are  only  formed  with  secondary  amines,  i.e*  those  with 
an  imide  hydrogen  atom.  From  tnis  ne  concludea  that  the  secondari- 
nitrogen  of  pnenjlhi'drazine  is  the  one  to  which  the  nitroso  group 
is  attached.  Ke  also  pointed  out  tixat  unsymmetrical  secondary 
hydrazines  which  iiave  no  imide  hydrogen  atom  do  not  form  nitroso 
nyurazines,  uut  are  promtly  decomposed  on  treatment  with  nitrous 
acid.  In  nis  opinion  txxe  lormation  of  pxierijlazide  on  treatment 
of  nitroso-pxxenyinyurazine  with  dilute  alnali  snows  that  water 
splits  out  between  txie  nitroso  and  txie  amino  group  , again  showing 
that  the  nitroso  group  is  attacixoa  to  tne  seconuary  nitrogen  aoora, 

Tixieie'^*)^^’ ^ in  view  oi  new  evidence,  did  not  entirely  ; 

agree  witn  Fiscxier,  He  consiuerea  that  tnere  naa  to  be  some  sort  of 
tautomerism  to  account  lor  some  oi  the  facts  oDserveu,  If  txie  i 

structure  of  ni troso-pxxenylhyurazine  were  accurately  expresseu  by 


NK2  unuer  all  conuitions  it  would  oe  hara  to  avoid  the  as- 
wU 

sumption  that  the  formation  of  a sodium  salt  is  due  to  the  activa- 
tion of  one  of  txxe  two  hydrogen  atoms  of  txxe  amino  group — an  as- 
sumption that  seems  ixardly  reasonaole,  Furtxxermore  ixxiele  pointed 
out  tnat  txxe  quantitative  elimination  ox.  i\i^O  from  txie  phenylhyara- 
zine  derivative  uj  simple  heating  is  uiflicult  to  understand  on  the 
basis  of  the  Fiscxxer  formula  alone*  Moreover,  ooth  oenzaldehyde 

and  acetaldehyde  uo  not  react  normally  with  nitroso-pxxenylxxydrazinoj 

G0H^-iN-W=CH-CgK5  34  3i' 


but  yield  the  tetrazine. 


C6H5-iM-i\i-CH-CbH5 


and 

' H *7  ^ 


r 


■’  i, 

»■  I 


' #kW  A 


r y 'll 


:'  -\ 


-..iJ  1H 

. ■*  V, 


\i; 


!**»•  lU  'I 

-< 


iv 


I V C l (,■  ' < ~ •■ 

*••  H"'  V.,  V 

'n^riWMUv  •(»• 

4*^'  , 


'■ ' _.  ,V'‘  L ' oq  t . _ , 

i cpr  <5*vifti  .[Tirt 


, , u 


C l 'Jfr 


A 


,•'4 


.iS,  ivr  ; iVi.  , c ■ 


Cw  cji.  ,j^  ' r«* 


c . 


^!0J| 


.'I  I 


) ^ 

■<  « ( . X . M IJ  £ 4 i .]  jg^jt 


14 


respectively.  UurLius  ±ound  tnat  ni troso-uenzylhyarazine  wiiicn  also 
xorms  a souium  salt  ana  in  OLner  lespecLa  is  closely'  related  to 
nitroso-piienjlnjarazine  in  properties  xorms  normal  condensation  pro- 

r-»  -T 

ducts  with  the  same  alaenju.es. 

56 

Tiiiele  found  that  the  elimination  of  NgO  is  common  to  doth 

the  aromatic  and  the  alipnatic  primary  n^urazines,  while  not  a trace 

of  eliminated  from  the  secondary  nyurazines  such  as  nitroso- 

37 

di-denzylnyarazine . Tniele  and  Sieglitz  explain  tne  reaction  of 
denzoyl  cnloriue  on  nitroso-phenylnydrazine  by; 


hO 


^ ^ JMO  0 ^ 


bnuic  ^ 

bp  gob 


H1M02 

All  Of  tnese  facts  coniirm  liscner’s  conclusion  that  the 

nitroso  group  is  attached  lo  the  secondary  nitrogen  atom  as  one 

form  of  tne  nitroso  compouna,  but, to  explain  tne  lormation  of  NgO 

ana  other  reactions  observed,  it  appears  tnat  we  nave  to  agree 

witn  Tniele  in  nis  assumpuion  txiat  anotner  form  oi  the  nitroso 

^ 56,57  . , 

compound  consisLS  of  a tnree  membereu  ring  wnich  exiscs  as 
an  intermeuiate  form  in  some  of  tne  reactions  encouniered . The 
formation  or  aziaes  ana  the  elimination  or  if  0 from  nitroso 

(a 

hydrazines  woula  then  ue  explaineu  by  the  following  steps; 

K-N — NHo^: — » R“W— -N-K  < — ) K-NK-W-H  ^ KNH 

NO  ^ n5h  wo  2 2 

hamberger  suggested  yet  anotner  lorm  wnich  may  exist  as 
a tautomer  of  tne  original  f'ischer  formula,  JPecause  iie  found  tnat 
ni troso-pnenylnyurazine  forms  a copper  salt  wnicn  on  treatment 
witn  either  acetic  aciu  or  ammonia  yielus  a compounu  of  tne 
formula;  or  G^n^-iii-hUn.  Kizis  , one  oi  rhiele's 


4 


15 


stuaenLs^  poinLeu  oul  unaL  Lue  reaaj'  trans formation  oi' oC-nitroso- oc- 
benzyl-^  -metnylhjurazine  io  <-nitroso- oC -methyl-j3-benzyili^  urazine 
as  well  as  the  lormation  of  o(-nitroso- oC -methyl-J3  -Denzilidineiiydra- 


zine  by  oxiciafion  of  o( -niLroso- o(^  - benzyl- -methylnyurazine 
ai  l orbs  a sLrong  proof  of  Lhe  existence  of  one  three  tauoomers 
mentioned,  since  Lne  rearrangemen os  aoove  may  tnen  be  readily 


shown  by  one  following  reac Lions  ana  rearrangements; 


G.H,  -GHo-N  — WfiCh^- 
o 5 ^ X,-.  o 

i'lO 


G^n  -Gri^  -i'j iM-Gh-r 

i'jQn 


-X^CeH^-GKg-N^N  -GK^ 
N OH 


G .H(--GKo-NrH  — GK„ > C Hj- -GH. , -HH-N— CH 


The  sodium  salts  oi  sucn  compounds  can  Lixen  ue  expressed  by 


either  of  tixe  following  Lxxree  foimuiae; 

(1)  (2)  = (5) 

HO  Na  hONa  hOHa 

It  is  very  uixficult,  if  noL  impossiule , lo  uetermine  at  the  present 
time  whicn  oi  tnese  turee  possible  forms  exist  ana  which  is  the 
one  tnat  is  found  as  one  major  produco  at  any  Lime.  Ghemical  reac- 
tions offer  little  iiope  ior  Lne  soluLion  oi  tnis  problem  and 
physical  meLhoas  nave  so  lar  not  seen  developed  far  emoLigh  LO 

warrant  tneir  use  in  tne  case  of  ni orogen  compounds  of  onis  type, 

P 

An  interesting  confirmaoion  of  the  assumtlon  that  bhe  oxime 
form  exists  in  Lne  case  of  nitroso  hydrazines  is  brougxxo  oul 
tnrougii  the  fact  Lnat  seconucxry  niLroso  nyurazines  give  an  in- 
tensive blue  color  witn  ferric  chloride  in  aqueous  solution,  a 
green  color  in  alooiiolic  toOluoion,  ana  a red  soiuoion  in  solution 

of  a non-dissociaLing  solvent  sucn  as  i^enzene,  cnloroiorm,  and 
"'iV 

ether,  Alternaue  uudiLion  of  wafer  or  aiconoi  brings  auOUL  Lne 


r 

t < 


if 


* ji 


i \ 


16 


corresponding  oiiocnges  or  color.  Tnis  uenavior  seems  to  indicate 
racner  aeiiniteiy  uuat  tne  color  is  due  to  a strong  ii^droxjl  ion 
formation  in  aqueous  solution,  a lower  one  in  alcoholic  solution, 
ana  tiie  aDsence  of  Luis  dissociation  in  such  solvents  as  uenzene 
ana  ether.  The  same  color  changes  are  prouuced  in  ihe  case  of 
the  nitroso  aerivative  csl  s^'mmetrical  aiisoprop^'l-h^'drazine  although 
the  color  rapidly  faaes  cecause  of  the  rapid  reduction  of  the 
ferric  salts  formed.  Tnese  color  cuanges  can  nardlj  oe  understood 
on  tne  assun^^tion  that  tne  I’iscner  iorrrn*ia  is  the  only  form  in 
wnich  tiiese  compouiius  exiot.  Aituough  Lue  proof  is  not  y jt  con- 
clusive it  appears  very  liii.eiy  tuat  tne  salts  of  nitroso-hydra- 
zines  exist  eitner  as  formula  (2)  or  as  (o)  page  16,  while  the 
ni  troso-uyurazine  as  sucii  may  normally  exist  maixily  in  the  form 
assume a Cy  liscner. 

Nitrous  acia  reacts  wl  symmetrical  disuhs ti tutea 

iiyarazines  in  two  aiiferent  ways.  In  most  cases  the  mono-nitroso 

hy 

compound  is  formed  . In  some  cases,  nowever,  especially  where 

acia  salts  of  the  base  are  staule,  the  dinitroso  compound  is 

iormed  if  an  excess  of  nitrous  acid  is  employea.  ^he  mono-nitroso 

derivative  may  also  be  formed  by  tue  alky la  Lion  of  the  correspond- 

. , .69 

mg  primary  nitroso  nyurazme 

The  more  interesting  oi  the  two  types  of  ni  trsos<>  compounds 
of  symmetrical  nyurazines  is  the  ui-nitroso  derivative  because  it 
decomposes  readily  to  iorra  an  azo  compound  and  2 mods  of  nitric 
oxide.  Tuis  reaction  takes  place  even  in  tue  cold  in  tne  case  of 
tue  dinitroso  aerivative  of  uydrazome thane. 


17 


In  Liie  oaae  oj.  s^mmeLrical  u.iisopropj  injurazine,  ohe  mono- 
nitroso  oompouau  xias,  t>o  i'ar,  ueen  Lhe  only  nioroso  (jompound  iso- 
laLed,  Tne  xact  liiai  inere  is,  in  txie  case  oi  the  uerivative  pre- 
pared wiLh  acet-ic  aoiu  and  an  excess  oI  sodium  nitrite,  always  a 
consiaeraoie  amount  oi  evolution  oi  gas  even  alter  tiie  excess  of 
acid  lias  been  neubralized  may  inulcate  tnat  there  is  always  form- 
ation of  a small  amount  oi  tue  di-nitroso  compound  whicn  would 
prouauly  be  very  unstaole  and  decompose  before  it  could  be  isolated 
Cooling  slows  dov.n  tne  gas  evolution  out  uoes  not  stop  it,  and  on 
warming  tue  reaction  continues  at  tue  former  rate  for  several 
hours  oeiore  linall^  slowing  uown  ana  stopping  entirely. 

The  properties  oi  tue  nitroso  compound  agree,  in  the  main, 
with  tuose  of  ooaer  nitroso  compounds  described  in  tue  literature. 
The  intensely  olue  color  with  ferric  cnloride,  and  the  Lieberman 
reaction  are  louiid  uere,  as  in  otuer  nitroso  compounds.  Peculiarly 
enougii,  however,  nitroso-Sj'mmetrical  diisopropyl-iiydrazine  yields 
a sodium  salt  when  treated  with  a concentrated  solution  of  alcohol- 
ic sodium  hydroxide.  It  is  impossible  to  say  at  this  time  v;nich 
01  tiie  structures  advanced  for  such  compounds  (page  15)  is  the 
most  probable  one  for  this  sodium  salt,  but  it  seems  reasonable  to 
hold  tnat  the  oxime  structures  auvanced  bp  rhiele  and  hamuerger 
arc  more  likelp  to  be  tiie  ones  iound  uere  uuan  tue  xormula 
assumea  uy  i-iscuer, 

Keuucbion  of  one  nitroso  uerivative  leads  to  ammonia  and 

symmetrical  ui isopropyl-hydrazine  instead  of  to  tue  amino  cora- 
CK.  /Ch^ 

pound,  Gh-i,M“NK-b;H  • 

CHJ'  hKg  CH5 


" ■ :0rsnir^. 


T’^^  j/tr 


*jir;i 


w J™ 


IWf  il  ■■' 

^ tti'#  - 

' 'f*  ■ -?r  ■.. f >,.4^  j 


' ■ ' ' . ' ■'  ' ' ■'4 

^ I^.  .;. ';^  ' .'  'h 


• ' *.■•  -^v-j  ^ •*> , i. « A \V*5;Ati  «»  a Set  •-'Xi 


••It  jk-/'* €| •.  '')'•».'•<■■•  .■  '■  "Vf  •’5*'‘■^^^^^i^e's^&:; 

^ !f  ■ 

KS 

i * ' * t#  ^&Jijltti  'V, ^ X -'.’  v'.ti 


•i^ 


. /,  1 o*.r^  7, ' i 3- 

. 'inv.  ,.,iM 


BR,  , ^''  ^ *.  ■ , ,.  li"'  . '* 

;.u.  a*. # 1^  i;f44'«^0'‘'l^  . li 

'.t  ; Vj.  - . ;fr- 


- '^<; 


r 


l.£ 


iJvJ  • A '.t.-'.'j  V-UiUt 
l*  ^ ' / i '^f\ 


iii'*'. 


J.L/iJU 

/I  . •■- 


ii  -'irx-  V T . 4.  ^ , , r '^  * 

,K  W^iT*-.;  ./>*■  #^'l^4ii'^'  , ,-r  ^ ;,  y ^ J i/L?/! 

i t ' -4, j ,.  »i  M V ^u  %fk^i  t.fii;,  $k'  *:i-- ' 

■'  ‘ > . V-'  " ' ■'■  p.  ' .. 


:t 


j , ;j 

^ 3^  I > .<>/'_■'  t i f'  kiiihL  »-  t i r ■ ■ 


■JQ® 


- - “^^ 


A Vt 


u 


- IB  - 

Wiien  tne  ury  lijarochioriae  oi  tne  nj-arazo  oomp^u  is  mixed 
wiLu  an  excess  of  copper  oxide,  a peculiar  sweeLisn  odor  is  oDserved 
in  auouo  15  minutes.  In  the  course  oi  an  uour,  ii  tlie  excess  of 
cooper  oxide  is  not  Loo  great,  some  moisture  may  be  observed  on  the 
crystals,  by  nexu  morning  the  mass  is  uistinctly  moist  while  the 
odor  lias  become  much  more  nouiceaule.  A! oer  5-4  days  the  mass  is  so 
wet  thau  it  may  ue  pourea  irom  txie  flask  in  wnich  the  oxidation 
tooK  place.  After  anotxxer  day  or  two  tixe  reaction  mixLure  in  tiie 
original  flask  is  distilled  in  a water  uath.  If  the  xieat  is  applied 
slowly  the  ruby  red  crystals  oi  an  unstable  copper  sale  wxxich  is 


firsi  ouserved  on  the  seconu  or  ixiiru  uay  of  ixxe  oxidation  process, 
are  found  to  change  suddenly  from  red  to  greenish  wniie  at  8B.5°. 


At  oxxe  same  time  i.ue  oxidation  pfoauct  distills  over  as  a yellow 
oil  01  a nauseatinglj  sweet  oaor,  from  y2-9B°  tiie  disbillate  is 
composeu  largely  of  waier  wxiich  xorras  a separate  layer  underneath 
txxe  oil  layer* 

The  yellow  liquia  is  reaaily  uried  over  calcium  chloride 

and  is  pure  afier  one  f ractiona bion.  The  analyses  and  tiie  molecular 

weigiit  deuerminauions  show  that  the  compound  has  the  empirical 

iormula,  G-H-.  This  lormula  applies  to  2 ,2  ’ -azobispropane  and 

b -L4:  ^ 

to  the  tauLomeric  acecone  isopropyl-hyurazone , The  determination 

of  the  structure  of  tixis  compound  constituted  one  of  tiie  most 

diificult  parts  of  this  investigation. 

Aromatic  azo  compounas  have  been  known  lor  almost  a 

4u 

century  and  have  been  txiorougniy  stuuied, 

hixed  aromatic-aliphauic  azo  compounas  are  known  and 
are  interesLing  uecause  txxey  of uen  cnange  over  very  readily  to  the 


- ly  - 

45 

tautomeric  sLrucuure  • 

Kyurazines  oi  tne  tjpe  represented,  by  symmetrical  di- 

benzylnyurazine  are  usually  oonsiaered  as  alipiiatio  hyarazines 

although  their  properties  uiTfer  considerably, in  some  cases, from 

tne  purely  aliphaxic  compounds  represented  by  such  compounds  as 

symmetrical  ui-meUiyl-nydrazine  and  Lne  hydrazo  compound  prepared 

in  txiis  investigation,  ihe  uiiierence  in  properties  is  probaoly 

due  tO  tne  proximity  oi  the  phenyl  group.  Symmetrical  hyurazines 

of  ail  types  tenu  to  yield  stable,  slightly  colored  or  colorless 
, . 44 

azo  derivatives, 

hone  OI  the  azo  compounds  so  far  xnown  are  very  closely 

related  to  Lhe  product  to  be  expected  on  mild  oxida.tion  of  the 

hydrazo  compound  derived  from  uimetiiyl  xetazine,  Azo  metnane  is 

is  tne  only  homoiogue  of  2,2 ’-azobispropane  known  so  far,  IL  has  a 

very  faint  straw  color  in  txie  liquid  state,  but  is  colorless  as 

59 

a gas  (hence  often  erroneously  called  a colorless  compound).  As 
is  indicated  by  a boiling  point  of  only  1,5°,  its  properties  may 
differ  considerably  from  tiiose  of  tne  higher  homologues  because 
it  is  a well  Known  fact  that  the  properties  of  the  first  members  of 
a homologous  series  are  often  markedly  different  from  those  of 
member  witii  five  or  mors  carbon  atoms. 

The  light  straw  color  tnat  is  observed  in  every  specimen 
prepared,  tiie  neutral  reaction,  tiie  immiscibili ty  witn  water, 
dilute  alkali  and  diluLe  acid,  and  tixe  unexpected  stability  Lo- 
wards  nyurolyzing  agents  wnicn  maxes  it  necessary  to  employ  a 
solution  of  1 part  of  water  to  1 part  of  concentrated  hyarociiloric 
acid  if  tixe  hydrolysis  is  to  oe  completed  within  an  hour  of 


n •’  i'i  . 


i : ' ‘ ■ 1 1 i. 


■>  * 


» . ■"?  ■ -lAi  4llN 

'• 

■fc.  \ 

jj|j3  j 

^ lU*  ^ 

. ^-  . ■ 
'•tar"  ,1’  ".'  ’'V  v^>  •’•i.jtrJ 

■'.'5  i 

n .»  \ 

1 ykc^Xu 

(>  X ,.  t- 


» j C ■ ' » "A  ^ ” " 

,fr  li.  lili  V >•  { • •' 


..  I 


vnc'. -rJ'  ..vp  - / 

- I 

■ . .-  .vl'i’  ...  I 


e.i.^ 


• I ••  / 4' 


tU'- 

.:  . w 1 . ■'■.  ■ • I ■ 

i o .:.  -ijU  ' if-;i.’u 

■ ' ‘ ■ ■ 

< ' . . > 

1 

i ■ .-.■V)  a^i'JU.y-  'A'/' 

-^Tvrq 

c 4 *y 

' 

. ,y4|4ii  * Stl  X 

'■0  *C\A..-l' 

- . , ..a  C.i. 


xC  1?»  li 


. '.fi  .•>  ■ 1 


. f 


'.oliri-i,  . 


. W w 4 


k 


'■.ffjJ. 
- 1 


■ .v'ir.-o  ‘ip, 


V,  '; ; ! 

...  ••■. 


'-.i 


. . 1 

N 


^ UOT^iO'iS^ 


t '■* 


xi-  ^ ®JuXJ.Ai 
^ . ■'>•'■.  J 


. i ) . 


T n' 


I ■ 

i. 


. j ...  ; i.  V . IT 

J’/.  X 0 » i rTAK  i.' 


20 


boiling  unuer  reflux,  all  inuicaleci  ouab  lue  oxidalion  product, 
is  actually  tne  azo  compounu.  An  examination  ox  tne  t^-pe  of 
tauoomerism  snowed  tnat  tne  properties  mencionea, although  thej' 
led  to  a strong  presumption  that  Liie  azo  compound  nad  teen  formed, 
did  not  aosolutely  excluv:ie  tne  possibility  that  the  substance 
niigiit  be  the  hyurazone  in  spite  or  inaicauions  to  the  contrary, 
xhe  i allowing  uiscussion  snows  wnat  basis  there  was  for  any  un- 
certainty in  regard  to  the  structure  of  tue  oxidation  product. 

ae 

Alipiiatic  azo  compounus  tena  to ^ompose  in  two  different 
ways.  One  is  an  actual  aecomposi tion,  the  otner  is  a rearrangement. 
(1)  Azo  compounds  may  rearrange  from  the  azo  to  the  hyarazone 
structure; 

-CHg-hsb-n  »■  -Ch-h-hH-K 

(2)  Tiirougii  elimination  of  one  molecule  of  nitrogen  gas,  azo 
compounas  may  uecompose  to  form  hydrocarbons; 
h-Nsh-R  * K-K-/-  ^2 

Among  cases  so  far  observes  tixe  nydrazone  seems  almost  always  to 
be  trie  more  stable  form,  altiiouj^n  , in  the  case  of  symmetrically 
substituted  hyarazines  the  azo  is  usually  stable  enough  to  be 
isolated,  while  some,  lixe  azomethane  are  stable  enough  to  with- 
stand rather  nigh  temperatures  without  showing  any  sign  ox  re- 
arrangement to  tne  lijurazone  form. 

43a 

i’ischer  was  the  lirst  to  observe  a case  of  this  kind  of 
isomerism  wnen  he  notices  tnat  acetalcehyde-pnenylnydrazone  is 
formed  readily  wnen  phenylazoe thane  is  treated  witn  acids  or  alkali. 
In  many  C0.ses,  isolated  since, it  nas  not  been  possible  to  isolate 


It. 


, 'I. 


a ' sj  - ' t'  i. 


* 1': 


I » 


■■  c.V'j  likit 

* i»» 

^ : 'r;6xu  , . .'  : • 


f ^t< 


I 


» 


fLi 


r : .-r  sjaefe 


■| 


J 


21 


the  azo  compouna  txxau  is  supposed  to  De  an  intermeuiate  in  the 

oxi nation  of  a symmetrical  n^drazine  to  tne  hyurazone  Inat  is 

45 

iinally  isolaied. 

In  tne  case  of  uiphenyl  and  tripiienyl  metna^v?  derivaiives 
tne  azo  compound  is  also  not  stauie,  Put  in  ouese  cases  cLe  com- 
position of  the  final  products  shows  chat  the  second  type  of  de- 
composition of  azo  compounds  has  c-aken  place,  i.e.  nitrogen  gas 

3S 

and  a iiydrocaroon  are  the  products. 

In  Liie  case  oi  Kiscnner's  spuLhesis  of  nyurazones  of  tne 

. . 44 

type,  R-hH-h-R  , ine  in uermeuiace  azo  compound  is  nou  isolated  • 

Azo  isobutyric  acid  and  tue  dinitrile  irom  which  it  is  formed  are 

stable  uecause  tney  cannot  rearrange  according  to  oixe  first  Lype 

of  rearrangement.  Wiien,  ni^ver,  caruon  dioxide  is  eliminated  from 

, . . . 4lc 

tne  compound  it  rearranges  immeuiaoeiy  to  tne  iiydrazone. 

Wnether  tne  same  rearrangement  wouiu  taxe  place  ii  two,  in^teau  of 
one  mol  or  waroon  dioxide  , were  eliminated  could  not  oe  snown  by 
Tiiiele.The  compound  obta.ined  on  oxidation  of  the  hydrochloride 
of  2,2 ' -hydrazobispropane,  shows  that  the  rearrangement  would  not 
iiave  taken  place  ii’  'iniele  hau  been  able  to  eliminate  both  mole- 
cules of  carbon  dioxide  at  tiie  same  oime. 

irom  a consideration  of  the  rearrangements  just  discussed, 
it  may  readily  oe  seen 

^nat  a compound  wnicn,  like  the  oxidation  product  under  discussion, 
may  be  refluxeu  for  ixOurs  and  may  even  be  treated  with  sodium 
alcoholate  for  severul  uours  at  a time  at  110°  witnout  any  notice- 
able cnange,  mi^^iit  well  be  mistaken  for  a uydrazone  in  spite  of  the 
other  properties  mentioned.  Since  absorption  bands  could  not  be  de- 


IT’  > 


22 


tec ted  in  tne  visiDle  spectrum  on  examining  the  oxidation  proauct 
ior  sucii  bands,  ana  since  Lne  refractive  constants  for  nii-rogen 


in  compounus  nave  not  been  aetermined  for  compounds  of  txiis  typ® 
wii-n  sufficient  accuracy  to  make  them  useful  in  proving  cxie  struc- 
ture of  a compouna  fixe  2,2 ' -azobispropane , physical  means  did  not 
seem  to  offer  any  xxope  of  being  aole  to  prove  the  structure  at  all 


conclusively  by  their  aid. 

The  only  'lvw  f easily  methods  left  now  were; 

(l}The  preparation  of  a aerivacive  of  the  oxiaation  produce,  and 
(2)  the  preparation  of  tixe  xx^arazone  itseli  by  some  otxxer  metxxou, 
Oi  txxese,  tixe  xirse  gave  little  xxope  of  success  since  if  became 
apparent, after  a series  of  experimenes,  that  no  derivaeives  that 
would  be  of  value  in  proving  its  structure  could  oe  obtained  fron 
tne  oxidation  product.  Possibly'  sucxx  derivafives  may  some  day  oe 


prepared  by  mecxious  enat  were  not  tried  in 
metnod  xxelu  out  equally  small  nope  at  xirst 


fxiis  worn.  Txxe 
as 

, in  as  mueix. 

A 


second 
in  spite 


of  numerous  trials  under  varying  condifions  no  xxydrazoixe  could  be 


isoiafea  alfxxougii  the  ouor  of  a new  compound  coulu  be  nofeu.  in  a 
numuer  of  f rials. 

ji  ^ 

heddelien’s  metxxod  of  condensing  aromatic  amines  with 
aldehyues  and  ketones  fo  lorm  aniles  proved  to  be  the  only  metxxod 
that  gave  a good  j'ield  oi  tiie  h^'drazone. 

Zinc  cxxloride  is  very  oi  ten  used  as  a dexiyurat ing  agent 
since  it  is  one  of  txxe  most  hygroscopic  of  suustances.  Moreover, 
txxe  vapor  pressure  of  water  over  moist  zinc  cxxloride  at  25*^is  only 
0.85  mm  while  at  50^it  is  still  only  2.99  ram.  Since  txxe  adsorbed 


'-'.  . *'  V-I/  »?i7  hit. 

e ■ * )■■•  I 

) ~ '■  ■ I 

s4U 


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V ■■  , iL  •'Ji|||B.  i ' m 

t'  ■'  ■ 1,^  . >7  , , *^''■  f'V-'*'^ 


\ ■'■  •’ 

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t .'  •/  .> 

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,p"  '1^'  \iij 

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Ai^C  ■ -■  •^♦V 

■ Vi  TH^I^L.  > 

4ll  /-j^'',  ; '.  . '■■  ■ ' . ■■.^  '5'^,y  ■!  : ' ^ y ■\'^  ' ■’"  ^ 

( *)  ■ ^tJT*  *i,,'  « ,1  . V 


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Lf  _ , 'J  .vl:.,  ,.  • V,  A .«  J,,  , :,vi^ 


. Ai./.  i c i -^t’'i4  <J.pa  Hi*' *i'i-‘<3t'^'J e/s  ^<f ■f^ji;5r.>r'Aii 

y^x  j.-.^-'  .'  »:  ■ . ■ ^'i  ■ ■ T ^. ■ r ,^A  i;t, 


l ’'^  •'■  ■■'"'  ^ ty  >. I .j;  t 

' ; . ''  2 ■'■'■ ' ' ’ » •.  v'  I ■ ‘ ^ '^>  ■ ^- 

V i^i-.  a^is 


V V.  . 


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■w% 


— . . '«.yj‘  J’’  , VVy’-'J  ilBi.  : '^»*  ■ ■ ■' 


‘ J '*^i'‘ ■ •" ^ ? ‘1 ■ - '•  * •“ ;'f  ^ •' '« 

'^  ■ ..  *Jft.  • . It  ■MiiJ>,  i J.f  ^ ','^*^  * *'■  t^' 

'. . . r.  ^-"•'i  - . 'ji ' 


"W 


25— 


waLer  is  noL  given  oif  unoil  one  meioing  point  is  reacheu  at  2yu- 

o , . ' . 

297  , tuis  salt  , in  manj'  cases  , oe  used  as  a aehyarating 

agent  irom  wnich  one  tiie  dried  substance  may  oe  di skilled  directly 
Naourally, une  tendency  of  zinc  cnloride  to  form  complex  salts  with 
amines  and  many  otner  substances  must  ue  taxen  into  account, 

Keddelien  made  one  peculiar  ooservation  that,  in  the  pre- 
paration of  anileSjthe  zinc  cnloride  does  not  act  so  much  as  a 
aexiydrating  agent  as  in  me  capacity  of  a catalyst;  i.e.the  salt 

does  not  ’’bind”  the  water,  out  immeuiately  li cerates  it  as  steam 

o 

at  the  temperature  of  170-180  employed  oy  this  investigator  in 
his  condensations.  Tnus,in  the  preparation  of  benzophenone-anile, 
he  employed  l/40  mol  of  zinc  Cuioride  to  1 mol  of  eacn  of  the 
otner  reagents,  and  ^et  obtained  a very  satisfactory  yield  of  the 
anil  . Tnere  is  nere  tuen  here  some  sort  of  catalytic  action 
similar  to  tnat  of  iodine  when  it  is  used  as  a condensing  agent 
in  tne  preparation  of  the  same  type  of  compounds. 

makes 

Anotner  interesting  observation  tnat  Heddelien^n  tnis  con- 


nection, is  tne  fact  tnat  tne  zinc  Culoriue  acts  as  a catalyst  only 
in  cases  in  wnich  the  uases  concerned  form  a definite  compound 
with  the  zinc  salt.  If  sucn  a salt  is  not  proauced  the  zinc  chlor- 
ide acts  simply  as  a denyarating  agent;  one  moi  oi  uhe  zinc  salt 
must  be  used  to  one  mol  of  the  uase  and  tne  reaution  must  be  run  a 
a nigner  temperature  than  in  tnose  cases  where  the  zinc  salt  acts 
as  a catalyst, 

4? 

The  work  of  2 oeppritz  and  Dimrotii  ma^^  tnrow  some  light  on 
the  mechanism  of  tnis  type  ox  condensation  reaction.  They  claim 


I 

i 

I 


I 


i; 


I 


! 


• »r* 


24: 


i/iiao  anile  (and  presumaul^  also  u^drazone)  xormaLion  takes 
place  in  ovvo  SLeps; 

\ ^ 

/C3O  4-  Kj^N-K  > C— K-k  > ^C-K-k  (k  = aromatic.) 

k H H n -f- 

K^O 

Tney  isolated  tne  intermeoiate  proauct.  It  is  very  easily  decompose 
ed  uj  heat  eitner  inco  tue  original  subsLances  or  into  tne  de- 
sired anile,  xne  lact  tnat  tne  lirsL  step  coulu  not  be  ouserved 
in  the  preparation  ox  ace Lpne-isopropyl-hydrazone  may  mean  that 
in  xnis  case,  Lnis  suusLance  is  so  unsLauie  cnat  it  immediately 
eliminaLes  wacer  and  cixanges  co  tne  hyarazone  even  at  40-60^  at 
which  this  reaction  is  run  with  besc  yields. 

Contrary  to  the  experience  oi  neudelien  who  naa  to  heat  nis  i 
reaction  mixtures  to  170-180  uegrees,  it  is  found  tnat  tne  re-  ' 
action  mixture  of  acetone,  zinc  cnloride,and  primary  isopropyl 
iiyarazine  heats  up  spontaneously  and  has  to  be  coolea  to  xeep  tne  I 
temperature  irom  rising  auove  40-b0  degrees  with  too  much  loss  of  ' 
acetone  on  boiling.  Zinc  chloride  reauily  forms  a compound  with 
the  primary  hydrazine,  but,  as  only  a small  amount  of  zinc  salt  is  : 
employed  the  amount  of  complex  salt  lorned  uoes  not  greatly  lower  : 
I'he  yield  of  nyurazone  obtained.  The  product  is  distilled  directly  ' 
witnout  attempting  to  filter  tne  zinc  salts  that  are  found  in  the  ' 
mixture.  There  is  a slignt  lowering  of  yield  due  to  this  dis-  1 

tillation  xrom  tne  salts,  out  this  loss  is  not  as  great  as  that 
uue  to  attempiing  to  filter  off  the  gelatinous  zinc  salts  tnat  are  ■ 
iormed  in  txie  reaction,  me  pro^auct  Outaineu  on  distillation  is 
mixed  with  an  equal  voiume  of  ury  etner  and  dried  over  anhyurous 


25 


soaium  sulphate  for  5-4  uays.  uistillation  now  gives  a yiela, 
sometimes  as  nign  as  of  the  calcuiaLea  yield  of  the  color- 

less hydrazone  boiling  between  125-and  135°.  On  refrac oionation  of 

this  part  almj::.t  ail  of  the  producL  comes  over  between  132  and  154°, 

a 

Thus  prepared  the  hyarazone  isy^colorless , basic, liquid  witn  sting- 
ing menthol  odor.  It  is  extremely  sensitive  lo  any  nydrolysing 
agent,  even  water  reauily  nydrolyzing  it  into  its  original 
components.  Ixiis  explains  vnhy  it  was  so  difficuiu  Lo  obtain  tne 
product  in  Lhe  earlier  experiments  made  in  an  attempt  to  produce 
tnis  hydrazone  as  a part  of  this  investigation.  All  attempLs  to 
make  the  benzoyl,  tiie  phenylmustard  oil,  the  cyanic  acid,  or  the 
hyarocyanic  acia  uerivauives  of  Lue  h^arazones  failed  for  the 
same  reason.  Tne  prouuct  obtainea  was  always  tiie  derivative  of 
tne  primary  nyurazine  — one  oi  tne  ny aroly sis  products.  The  hydra- 
zone is  the  lirst  one  tiiat  has  been  isolated  among  the  purely 
alipxiatic  series  of  nitrogen  compounus  while  the  azo  compound 
is  the  second  azo  compound  tnat  nas  ueen  prepared  in  this  series. 

The  azo  and  xiydrazone  stand  also  as  the  first  case  in  wnich  both 
txie  azo  and  txie  hydrazone  corresponding  to  a single  aliphatic 
symmetrical  ixydrazine  nave  been  Isolated. 

A comparison  of  txxe  properties  of  txxe  two  tautomers  leaves 
no  doubt  as  to  the  structure  tnat  must  be  assigned  to  each,  For 
convenience  these  properties  are  arranged  in  tabular  form  as 
Table  I on  page  26., 


26 


TABLii  I • 

Tabular  Arrangement  ox  tne  Most  Important  properLies  or 

2,2 ’ -Azouispropane  and  Acetoneisopropyl-Kydrazone , 


Property  — — 2,2 ‘ -Azobispropane  — Acetone-Isopropyl-Aydrazone 

Color  — _ _ rainL  Straw  — — _ Colorless 

boiling  Pt,  — — 68.5^ — _ _ _ 132-4° 

Density  t/4  — — - .7408  — — — _ ^ ,8223 

Iwol.Wt  _ _ _ _ 114  (110,119)-  _ - 114  (106,108,104) 

Mol,  Volume  _ _ _ 154  — _ _ _ _ 138.7 

^ (Abbe)  _ _ _ lo3890  _ _ _ _ _ 1.4560 

Carbon  fa  (63, lo  Calc)_  63.18,63.02, 63.02  — 62,69,63.00 
Hyarogen/o(  12 ,28  “ )-12,03,12,0b,12,46  — 12.47,12,56 

Hitrogen;>i(  24, 56  '•  )-  24,67  — _ _ — 24.98,  24.34 


Odor  — _ _ _ 

Synthesis 


Nauseatingly  Sweet _ 

Oxidation  of 
GHv 

CH3 


Stinging,  ken  tiiol 


CKv  /GH'i- 

CH3  ■ ''CH3 


behavior  towards j 


Water  _____  Insoluble  _ _ _ _ Soluble. Hydrolysis 

Dilute  acids  — — - — _ _ _ » 

Dilute  base  — — “ — — — — Solution  and  slower 

hyurol jsis 

Gone.  Alxali  and  Heau- Partial  hearrange-  — ho  change  to  azo,  any 

ment  Lo  ii;iurazone  conairions  . 

heauction  _ - Sasily  to  Hyarazo  basily  to  Hydrazo 

Oxidation  — _ - Staule  oruinury , weak.  — Decoraposi tion.ned  color. 


I 


c 


I 


I 


c 


- om 


i 


I 

I 


tl 


■I 

- 1 


27 


VVLen  one  azo  oterivacive  ox  symmetrical  aiisopropyl-uydra- 
zine  is  uoilea  un^er  refiax  witn  b0;50  hydro'cnloric  aciu  and 
wauer  one  supernatant  oily  layer  of  azo  compound  gets  thinner 
and  tninner  and  aiLer  about  30  minutes  uisappears  entirely. 
After  auout  30  rainuLes  more  the  tixe  condenser  is  arranged  i'or 

distillation  and  tne  aceoone  distillea  oif  . Tne  rest  of  the 

the 

liquid  is  distilled  off  under^vacnum  of  a water  pump  until  the 
resiaue  has  uecome  syrupy  . If  the  syrup  is  now  coolea  in  an  ice 
oatu  the  wnoie  mass  turns  solid.  The  fine  crystals  are  filoered  off 
rapidlji  uy  suction  and  the  xiltrate  concentrated  some  more  ana  i/ne 
same  procedure  repeateu  unoil  only  a few  c.c,  of  filtrate  remain, 
Xhe  last  residue  of  one  iiydrochloride  of  primary  isopropy^l-ixydra- 
zine  may  be  removed  irom  inis  filtrate  now  by  adding  a few  drops 
oi  alcohol  and  several  c.c,  of  etner,  Unlixe  the  nyarochloride  of 
the  symmetrical  nydrazine  ihe  resiuue  snoula  noi  ue  evaporated  to 
dryness  because  the  iiydrochloride  apparently  uegins  lo  decompose 
lefore  it  crystallizes  out  of  a syrupy  solution  like  one  one  ob- 

r . • . 

tainea  on  concentration  of  ohe  hydrolysis  mixture.  The  hydrochlor- 
ide is  puriiied  by  rocrystallizaiion  irom  a very  small  amount  of 
alconol,  or  from  a mixture  ox  a very  small  amount  of  alcohol  to 
whicn  wnile  not  etner  is  auaed  to  tne  first  permanent  cloudiness, 
pie  hyarochioriae  prepareu  tnru  hyarolysis  oi  the  azo  compound  by 
2onc.  acid  as  described  above  is  very  hygroscopic , wnile  the  one 
obtained  by  either  of  tne  other  metnods  mentioned  in  the  next 
-wo  paragrapiis  is  not  hygroscopic  or  at  most  only  slightly  so. 

,30 bh  salts  yielu  tiie  same  case  on  treatment  with  a concentrated 
soluLion  oi  souium  iiydroxide,  probably  tne  iiygroscopic  salt  is 


2a 


tiie  acid  salt  since  iz  is  prepareu  in  one  presence  of  tne  fairly 
concentrated  acid  and  since  tne  aciu  salt  is  usually  tne  more 
ii^'groscopic  salt,  decause  oi  tne  aiii'icultj  of  wonting  witn  an 
exLremely  nygroscopic  salt,  no  attempc  was  made  to  analyze  tne 
ii^'groscopic  salt,  uut  the  neutral  salt  was  analyzed  and  proved 
to  de  normal. 

Primary  iso^.ropyl-hydrazine  is  also  obtained  wnen  the 
hydrazone  syntiiesized  above  is  nydrolyzed  by  dilute  acid  or 
even  by  water.  The  products  formed  here,  as  in  the  case  above, 
are  acetone  and  tne  primary  nyurazine.  Tne  acetone  was  identified 
in  each  case  by  means  of  the  benzilidine  derivative,  by  means  of 
tne  iodoform  test,  ana  finally  uy  the  souium  ni troprusside  color 

test. 

and  best 

A txiir^t^rae txiod  oi  preparing  tixe  same  primary  hydrazine 

consists  in  reducing  an  equi-moiecular  mixture  of 
acetone,  ny urocnioric  acid,  anu  njurazine  nyurate  in  exactly  tiie 
same  manner  tnat  the  symmetrical  aisuusti tuted  hydrazine  is  pre- 
pared. The  isolation  of  tne  ny drocnloriae  is  accomplisneu  in  txc 
same  manner  for  any  of  the  three  metnods  described. 


n 

The  simple  xiyurazone,  was  prepared  by  the 

metiiod  of  (jur tius'^'^,  but  is  too  unstable  to  be  used  in  obtaining 


the  physical  constants  of  tnis  class  of  nitrogen  compounus. 

tiie  dibenzoyl  and  the  phenyltniosemicarbazide  derivatives 
are  readily  prepared  and  were  analyzed  in  connection  witn  the 
positive  identification  of  primary  isopropyl-h^ urazine , 

primary  isopropylnyurazine  may  be  liberated  from  tiie 


//  ■ 


^ f 


f 


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M 


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J'  / . ' 


i' 


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t 


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.4'  ,/ 


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'^1 » *■  — 

dF  ir  ^ V 


lijurociiloride  in  tue  usual  manner  oy  vorj  concenLraLeQ  alKali 
which  causes  it  to  rise  to  the  surxace  to  lorm  a supernatant 
la^er  ol  jellovi/  oil,  Tiiis  la^er  is  then  uriea  lirst  witxx  i'useci. 
potassium  j.i^'Q.roxiu.e  and  Lnen  wiori  aluminium  amalgam,  Tne  amal- 
gam is  slow  in  ios  action,  ouu  the  case  is  tiiorougiily  dried  by 
it,  Melanie  sodium  is  found  to  be  satisfactory  and  ver^'  fast 
in  its  acbion  in  drying  tne  symmeLrical  hydrazine,  but  it  seems 
to  decompose  part  of  the  primary  liyarazine  if  an  attempt  is  made 
to  use  it  here.  In  every  case  the  base  produced  from  the  iiyaro- 
chloriue  constantly  gives  ofi'  oin^  bubbles  of  gas  even  Wixen  the 
i'ij drazine  hecs  been  tnorougiily  dried  and  dist-illed  in  an  atmos— 
piiere  of  nitro^^en,  kiscimer  reports  tne  same  beiiavior  in  the 
case  of  neptyl  ana  ocLylhydrazines.  No  satisfactory  analyses  were 
Obtained  on  tne  xree  base  and  a determination,  of  its  pxiy’sical 
constants  is  eviuently  useless  since  refractive  inaex  determina- 
tions show  Lnat  the  compound  gradually  uecomposes.  The  boiling 
point  is  between  104°anu  lOG^for  the  fresnly  uistillea  base.  The 
primary  hjdrazine  was  definitely  iaentixied  tlirough  analyses  of 
the  hydrochloride  and  oi  the  dioenzoyl  and  phenyltiiiosemicarbazidte 
derivatives. 


compounds  uifiering  in  only  small  details,  an  attempt  was  made  to 
determine  as  many  physicaj.  constants  as  possible  on  all  com- 
pounds tuat  are  stable  enough  to  permit  a reasonauly  accurate 


I 


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i,  >.iUjoJ  , . . ' . 

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'•  I 

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• j 

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t 

) 

j 


50 


de lerminaiion  oi  sucn  constanos.  Tiie  results  of  Lhese  ueLermina- 
Lions,as  far  as  completed,  are  here  offered  as  tne^  were  obtained 
witiiOuL  any  attempt  at  generalization.  It  is  hoped, uowever,  tnat, 
wuen  the  corresponuing  constants  xor  otiier  series  of  such  com- 
pounus  oecome  availaole  generalizations  of  value  maj  be  arrived 
at  • 


P. 


W'  * 


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*’  . 7 ‘ • ’ ■■/' 


^1^ 


50 


II  iiiXPJihiMiii'j  ixU-i 

DlkiiTHxL  ti-iilTAZINE.-  Tiiis  compouna  V\^as  prepared  according  to  tiie 

IBd 

method  oi  Curtiub  and  Zinkeisen  • _ue  -ieid  was  not  satisfactory 
at  any  time.  Vi/iiile  the  method,  as  given,  gives  a yield  ox  60-70;;'o 
ana  a slignt  moaix'icaLion  ox  the  metnod^i.e.  the  use  of  a 
excess  Ox  acetone,  increases  tue  ^ielu  to  70-75;3,  uhis  yield 
can  not  De  consiuered  satisxactory  in  view  of  the  nigh  price  of 
hydrazine  at  L,nis  time.  Tne  use  of  sodium  hydroxide  was  abandoned 
for  a while  and  sodium  carbonate  suostituted  for  it  buL  the 
yield  remainea  the  same. 

A rea  oil  was  always  obtained  as  a residue  after  Lhe  128- 
135^  fraction  nad  ueen  uistilled  off.  -ne  residue,  wnen  hot,  ig- 
nites on  contact  witn  air,  showing  InaL  tiie  substance  is  very 
easily  oxiutzea.  Tne  yield  was  coo  small  nowever  to  permit  iso- 
lation and  iuentif ication  of  che  oil. 

ATTEkP^'8  TO  iiEDUOS  xHE  KETAZINS. - Altnough  not  much  hope  of  suc- 
cess v/as  entertained  since  a number  ol  chemists  nau  tried  and 
failed  to  reauce  uimetnyl  xetazine,  anotner  series  of  attempts 

were  made  to  reduce  the  xstazine  with  common  reducing  agents 

through 

alter  tiie  reauction  products  v;ere  known^euuc  Lion  of  the  ket- 
azine  uy  a metnou  uescribed  later.  It  was  hopea  txiat  a knowledge 
ox"  tne  compouna  to  ue  expected  would  permit  cne  iuentix  ication  of 
a small  amount  of  riydrazo  compouna  tnat  mhgnt  nave  escaped  the 
attention  ox  earlier  investigators,  oouium  as  amalgam^ and  as  metal 
in  alconol;  alum-inium  as  amalgam^  and  as  xree  metal  in  the  pre- 
sence of  potassium  hyuroxiue,  gave  traces  of  reduction  compounds 


c*  . 


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-32- 


Out  tne  h^urazo  compound  could  not  oe  iuen tilled  among  them. 

Zinc  witn  various  acids,  iron  v^ith  acido,  ana  stannous  cnioride 

laiiad  to  give  anj  reduction  products  ol  the  ketazine. 

H 

3-lViETHiL- 5-dDviiii'KYL  PxKAZOLINii,  K-cf Yhien  a 

II 

lew  drops  ol  uenzojl  chloride  l\i  were  added 

i'j— H 

to  a lew  c.c,  ol  tiie  reuuction  mixture  ootaihea  in  one  ol  tiie 

unsuccesslul  attempts  to  reuuce  dimeoxijl  keuazine,  a crystalline 

compound  melbing  at  228-y*^  was  oucained.  iVielting  point,  appearance, 

and  analysis  showed  that  the  suostance  is  the  oenzoyl  uerivative 

ol  3-metiiy  1-b-uimetnyl  pyrazoline  wxiicn  was  originally  prepared 

Idh 

Oy  (jurtius  and  Zinkeisen 
Analysis: 

CalculaLed, lor  , N » 12,96^o 

round;  (humas)  N = 12.92;6 

Tne  acid  lormed  during  the  reaction  ana  dy  hydrolysis  ol  denzoyl 

chloride  is  thus  strong  enough  to  elfect  txie  rearrangement 

18d  18c 

SLudied  by  Curcius,  I’rey  and  Hoiiuian  , and  Iranxe  , 

AEjij'JriOw  Ol  riihxiiiixL  niiTAZiuEo-  Ss.ica's  metiiOd  ox  reduction 

by  iiydrogen  unuer  one  cataljtic  inlluence  oi  colloidal  platinum 

protected  ijy  gum  arable  was  ±inally  useu  with  oomplece  success 

in  tue  reduction  ol  tue  azine. 

Tile  apparacus  used  at  lirst  was  modelled  alcer  the  one 
25a 

descriseu  by  oxi oa  , but  was  later  modilied  so  as  to  be  less 
expensive  and,  especially, also  less  space  consuming.  The  use  ol 
the  troublesome  pressure  regulator  oi  Skita  was  also  avoided. 

Tne  linal  lorm  ol  the  apparaous  is  sixo.n  in  ligure  I. 


33 


Figure  I 


54 


Trie  open-cop  mercurj  manomeber  iias  a ientjCu  oi  200  cm  so 
that  a height  consiaeraoly  in  excess  of  180  cm  of  mercur^y  or 
over  two  atmospheres  excess  pressure  may  safely  be  employed  in 
bhe  apparatus.  The  capacity  of  the  tank, T, was  so  regulated  by  m 
means  of  a small  amount  of  distilled  water  tnat  was  placed  in 
the  bottom  to  seal  all  stopcocxs  and  at  the  same  time  to  pro -vide 
for  a flexiule  capacity  of  the  ^as  hoiuer,  Vuien  tuo  capacity  is 
about  20  liters  the  average  running  pressure  of  the  apparstus 
will  ue  suCii  that  the  drop  ox'  1 mm  in  pressure  is  equal  to  10  c.c. 
as  an  average.  The  exact  values  represented  by  a change  of 
pressure  of  1 ram  at  any  desired  temperacure  and  any  desired  total 
pressure  (atmospheric  plus  extra)  a^ e read  uirectiy  from  a chart 
made  when  the  tank  was  calibraced  with  the  wauer  level  fixed 
permanently.  In  tuis  way  it  is  possible  to  use  only  tlie  tiieoret- 
ical  amount  of  gas  to  complete  tiie  reduccion  desired,  tlius 
avoiding  incomplete  reduction  Liirougn  stopping  tne  snaker  too 
early,  or  over-reouction  tiirough  adding  more  hydrogen  than  de- 
sired. 

The  shaker  is  fastened  to  the  wall  by  a strong  hinge,  by 
tnis  arrangement  tiie  shaker  occupies  little  space  when  in  use, 
and  practically  no  space  when  not  in  use  as  it  may  be  folded 
back  against  tne  wall.  The  hinge  and  board  are  fastened  to  the 
wall  at  an  angle  oi  about  45  degrees  as  shovm  in  the  figure.  Tiiis 
angle  is  found  to  proviue  the  most  efficient  stirring  and  shak- 
ing when  Lhe  arm  is  swung  cacx  and  forth  by  a common  motor  driven 
snaker.  The  rocking  arm  oi  tu.e  shaker  is  xastened  at  tij.e  pointy n. 


-f 


• — 1* 


•*11 


X fa;  'iHi... 


. t/i.,  k. . / 

i '-TH/  .y 


'*••*“  V 


.*  t/jJUj  0 


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_ — •• 


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LUi  tr4 


j:  Tgs 


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- o5  - 

j.ne  i'labk  is  lasoeneci  in  a rapid  and  verj  satisfactory  aianner 
Dy  means  of  two  screen  door  springs  tnaL  are  hooked  into  rings 
behind  tiie  board©  To  prevent  poisoning  of  catalyst  due  to  con- 
Lact  of  tiie  liquid  with  Liie  brass  or  copper  tuoing,  the  coiled 
Luce  is  cemenLed  into  a piece  of  glass  Lubing  wnich  ohen  passes 
through  tiie  rubber  stopper  of  tiie  pressure  flask©  The  rubber 
SLopper  is  iield  in  place  securely  even  unaer  more  than  2 atmos- 
pheres of  extra  pressure,  by  means  of  the  yoke  damply© 

PEOCkhUKE.-  In  maxing  a reduction  run  for  tiie  first  time  tae 
acetylene  tank,!',  is  first  evacuated,  oiie  open  end  of  the  copper 
coil  , v¥W ' , ueing  closed  bj  lasuening  into  tae  empoy  pressure 
ilask,  Vhien  txie  pressure  aas  dropped  as  low  as  the  wauer  pump  will 
take  it  (20-30  mm|-  the  tiiree-way  SLopcock  ,5,  is  burned  so  as 
to  connect  v/itii"G"'  instead  of  with  "v".  "C”  is  connected  to  the 
Hydrogen  cylinuer  by  means  of  a snort  length  of  ruboer  pressure 
tubing  of  not  too  great  strength  so  that  in  case  the  pressure 
is  accidentally  raised  too  high  due  to  carelessness  in  ma.ni- 
pulation  of  the  valves  or  to  stoppage  of  some  passage,  tiie 
pressure  will  ce  indicated  by  the  bulging  of  tae  tubing  and  the 
eventual  blowing  out  of  the  tubing,  liien  the  tension  of  the 
tubing,  as  ielt  by  tae  aand,  inaicates  taac  tiiere  is  a slight 
pressure  in  tae  system,  biie  gas  is  Lurned  off  again,  the  three 
way  stopcock  turned  back  to  ‘'V“,and  tae  evacuabion  repeated. 

Yaien  again  evacuated  and  refillea  wita  gas  until  a slight  pressure 
is  inuicaLed  by  tae  tuuing  leaaing  from  tiie  cylinuer  to  the 
tank,  the  vaive  2 wnich  iias  been  closer,  up  to  now,  is  opened 
ana  the  pressure  in  tae  tanx  permitLed  to  rise  slowly  to  a total 


56 


pressure  oi‘  aoout  2500  mrn  oi'  raercur^’.  Tixe  valves  1 anu  4 and  the 

stopcock  5 are  tiien  cioseu  and  the  xlask  disconnected  from  the 

tuDing  and  cnarged  for  tiie  run.  Tiie  usual  charge  consists  of  50 

100  c.c.  of  15^  hj'drochloric  acid, 
c.c,  of  ketazine,  100  c.c.  of  water, ^10  c.c.  of  a solution 

oi  platinic  cliioride,  and  .5  g of  gum  arabic  dissloved  in  hot  . 
water.  To  tnis  mixture  is  then  added  the  "seeding”  colloid  pre- 
pareu  eitner  accoruing  to  tiie  direcbions  of  oxiLa  hj  heating  a 
few  cubic  centimeters  ox  a palladous  chloriue  solution  to  boil- 
ing and  then,  v/hile  removed  from  tiie  flame , allowing  a slow 
stream  ox  h^-drogen  gas  to  pass  througii  the  soluLion  to  reduce 
the  mexal  to  tue  colloidal  state,  or  oy  parcially  reducing  2--3 
cc  of  chloroplatinic  aciu  hj  making  it  alxaline,  heating  to 
boiling, and  adding  a few  crysdals  ox  n^drazine  cnloriae  or  of 
tne  iiy urocnloride  of  symmetrical  diisopropyl-h^drazine  . As  soon 
as  the  mixture  uuurns  ulack  it  is  rapidly  poured  into  the 
pressure  flask  where  the  alkali  is  neutralizeu  by  the  acid  present 
The  flasK  is  tiien  connected  to  tne  system  again  and  evacuated 
until  tne  acetone  starts  to  boil.  The  air  is  tnen  sufficiently 
removeu  to  permit  ti^e  reduction  to  proceed.  The  gas  is  aamitted 
to  tne  flash  by  opening  valve  1 as  soon  as  possible  after  the 
valve  4 nas  been  closeu  to  cut  off  tixe  vacuum.  lx"  the  acetone 
vapors  are  perrniLued  to  condense,  in  any  amount,  in  the  coiled 
tube,  the  catalyst  may  oe  poisoneu  by  txiis  liquia  wnen  the  gas 
pushes  it  uach  into  Lne  flask  in  course  of  the  run.  for  this 
reason  tne  gas  suould  ue  Lurneu  on  us  soon  as  possiole  aiter  the 
evacuation  is  completed,  if  the  desirea  amount  oi  pressure  is 
now  in  the  system  tue  snaner  is  soarteu  ana  Ghe  total  pressure, 


i; 

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- 67  - 

ana  temperamre  read  and  recoraed, 

i*'or  a lew  minuLes  iirtie,  ii  anj , absorbLion  is  nouiceu. 
ir  tue  acetone  xias  oeen  properly  purified  aosorbtion  v^ill  start 
in  a few  minutes  and  grov;  steaaily  more  rapid  for  about  an  hour 
when  it  reaches  its  maximum  and  gradually  slows  down  only  to 
stop  enitrely  when  the  ketazine  has  been  all  reduced  to  the 
symmetrical  nydrazine.  Tnis  may  take  only  3-4  hours  if  no  anti- 
caralytic  suostance  is  present,  usually  Lnere  will  be  enougn  of 
sucn  substances  present  as  impuribies  so  maberially  slow  dOY/n  Liie 
run  so  thab  6-8  hours  are  required,  unless  bhe  snaKer  is  stopped 
alter  the  aosorobion  slows  down  noticeably  and  more  platinum 
solution  adueu,  Tne  rate  of  reduction  aepends  on  tne  amount  of 
catalyst  present  so  that  , presumably , the  reduction  could  be 
carriea  out  in  muca.i  less  tuan  3 nOurs  if  we  were  willing  to  use 
more  platinum  tuan  necessary.  Usually  one  additional  addition 
of  10  c.c.  of  cnloroplatinic  acia  suificeu  to  reduce  a regular 
charge  in  3-4  xiours.  In  som.e  sucn  runs  absorb  Lion  uook  place  at 
tne  rate  of  over  12000  c.c,  an  nour  for  over  a hour  at  a time. 

The  solution  in  the  flask  warms  up  considerably  when  reduction 
proceeds  as  rapidly  as  this.  If  it  uoes  not  heat  up  to  about  40  ^ 
it  is  advisable  to  place  a very  small  flame  some  6 a'  8 incnes 
below  the  flask  to  neat  it  to  tne  temperature  of  about  40^ 
at  wnicn  aosorotion ../takes  place  at  txie  maximum  rate.  Should  tixe 
temperature  in  any  run  rise  to  the  boiling  point  of  acetone 
the  reduction  wohld  be  materially  sloweu  down  because  of  the 
acetone  vapor  wnicn  woulu  not  permit  tne  nydrogen  to  get  in  con- 
tact witn  txie  liquid  rapidly  enougn  to  sustain  the  original  rqte 


of  reauction 


li  an  atterapL  is  made  to  use  'cn.e  acetone  of  commerce 
disappointmenLs  are  almost  sure  to  come.  In  airaosL  all  cases 
in  wnich  t,ne  acetone  is  lo  ue  used  in  caLalytic  reduction  pro- 
cesses it  nas  to  Pe  purified  to  make  it  suitable  for  use.  The  im- 
purity manifests  itself  curing  a reduction  run  by  preventing 
absorption  of  hyurogen  entirely,  ii  there  is  much  catalyst  poison 
present,  or,  in  case  only  a small  amount  of  anticatalyst  is 
found,  the  aosorbtion  may  start  but  almost  immediately  reach  a 
maximum,  far  oelow  tne  maximum  reached  wuen  pure  acetone  is  em- 
ployed, and  tnen  rapidly  arop  off  until  no  gas  is  ausorbed. 

. . ^ . 49 

jO  puriiy  Uiie  acetone  one  metuou  of  dhipley  and  Werner 

was  found  satisfactory.  If  sodium  iodide  and  acetone  are  refluxed 

for  an  hour  or  more  a very  concentrated  solution  of  sodium 

iodide  is  oorained.  un  cooling  the  solution  down  to  -10°  or  even 

to  -].5  ° . if  convenient,  tiie  sodium  iodide-acetone  addition 

compound  precipitares  out  as  large  reddish  needles,  Tliese  are 

sucKed  off  rapidly  on  a large  iiucuner  funnel  without  filter 

paper.  The  needles  are  so  large  that  they  do  not  pass  through 

tne  funnel,  me  needles  are  then  placed  inro  a distilling  flask 

and  tne  acetone  is  uis billed  off.  It  practically  ail  comes  over 

between  5b. 5 and  56.6  at  750  mm  and  is  apparently  now  entirely 

free  from  anticatpLly tic  acrion.  The  filtrate  and  tue  residue  of 

sodium  iodide  from  the  distillation  are  mixed  and  ano  'v.  . .r  small 

amount  of  aceu^n.  aude^.  Inis  mixLure  is  refluxed  as  before  and 

a seconu  quantity  of  pure  acetone  obtained  irom  it.  If  Lne  acetone 

as  obtained  fi’om  stock  is  fairly  pure,  the  puriiying  process  may 


If' 


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a fit  . 

,fjn  . CiO  C ■'  ■ p s. 

'■**  '.  ■ \ 

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I . - 1 J.  <■••  _ I ' . 1.  . . . 1 ' ,1 , t ■ ^, '-  i *4, 

■' c I ■ ->^-  - * • 

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- 39  - 

De  repeateci.  as  mucii  as  5-6  times  before  cleaning  the  iodide, 

TO  purify  tne  sodium  ioaide  so  as  to  be  able  to  use  it 
again  for  similar  work  or  for  other  reac --ions  the  acetone  is  all 
distillea  off  on  a wai-er  bath.  The  wee  residue  is  then  poured  into 
an  enamelled  pan  W’here  iL  is  lurLher  dried  by  g^entie  heat.  V/ii^n 
Lhoroughly  ur^'  txie  neocb  is  gradually  increased  until  all  organic 
mauter  nas  seen  carsonized.  Thus  igniceu  iL  is  ready  for  use  in 
acetone  purii  icaoion.  For  OLner  chemical  wor^v  it  must  obviously 
be  puriiieu  uy  recr^ stallization  before  use, 

1 A few  early  runs  were  run  using  the  mixture  of  ketazine 

water,  and  catalyst  as  descriued  on  page  37.  The  reduction  was 
lounu  too  slow  iiowever  and  ane  reuucLions  as  next  modified  gave 
better  yields  in  snorLer  oime.It  was  observed  that  one  addition 
01  Ciiioroplatinic  aciu  always  produced  a rapid  rise  in  absorbtion. 
Tiie  quesLion  arose  wnetner  Luis  rise  could  occur  as  suddenly  as 
it  did  if  tne  extra  platinum  audeu  were  the  only  factor  trial  in- 
creased the  rate  of  absorution  of  nydrogen.  A small  amount  of 
hy urociiloric  acid  was  next  lOunu  to  nave  tne  s:me  effect,  in  case 
no  anticataiysL  was  present,  as  tne  addition  of  cnloroplatinic 
acid.  By  adding  small  portions  at  a Lime  Lhe  time  of  reduction 
was  soon  cut  down  ta  less  tiian  a uay.  Tne  neAb  step  v/as  to  add 
tiie  tneoreLical  amounL  of  aciu, needed  to  salify  all  of  tiie  base 
formed  , aL  one  start.  The  first  run  failed  oecause  b^ie  platinum 
reiuseu  to  be  reduced  to  the  colloidal  staLe  unuer  Lhese  condiLions . 
In  subsequenL  runs  tne  reduction  was  allowed  to  proceed  for  a xew 
minutes  anu  Liie  auiu  tnen  ull  auueu.  at  one  time.  Tne  yielu  was 
practically  quanLiLative . 


- 40  - 

Since  Ine  resuiLs  snowed  tnac  Uie  aadiLion  or  blie  caicu- 
latea  amount  of  hyarocnloric  acid  in  one  'lot  . did  not  reduce 
tiie  yields  and  even  shortened  tue  time  requireu,  tue  question 
or  hyurolysis  Oi  tne  ketazine  was  eliminated.  The  next  step  xor- 
waru  was  txie  used  of  oa  mixture  of  acetone  and  hydrazine  hydrate 
instead  of  xetazine.  This  avoiued  tue  step  that  yielded  txie 
lowest  yield  --  tne  preparation  of  dimetnyl  keLazine.  2.2  mol 
of  acetone,  1 mol  of  hydrazine  hydrate,  and  1 mol  of  nydrochloric 
with  the  original  amounts  of  cnloroplatinic  caid,  gum  arable  and 
’’seeding”  colloid  now  constitutes  a regular  run  after  dilution 
wiLn  100  c#o.  of  uistilleu  water.  In  tnree  runs  on  wnicn  u.ie 
yieluS,Dy  Lnis  metnou,were  ouLained,  25  g of  nyarazine  hydrate 
tiie  i'oilowing  results  wer^e  outainea,- 

I.  25  g n^drazine  gave  78  g of  hydrochloride  in  4 nours, 

II. 25  g iiydrazine  gave  BO  g of  hydrocxiloride  in  5.5  ” 

III. 25  g hydrazine  gave  74  g of  hydrochloride  in  6 hours. 

The  salt  was  weighed  after  it  nad  been  recrystallized  once  from 
alcOiioi  and  uad  uean  x^ept  on  paper  ovei-  night.  Its  melting  point 
was  107-8  unsharp  for  eacn  baten,  a cnlorine  ue terminations 

oy  Mohr’s  meti.oa  gave  23.8;^y  Cl,  anu  titration  witn  n/10  iouine 
gave  an  average  purity  of  for  the  salt.  These  show  tnat 

the  salt  was  practically  pure  anu  tne  yielu  almost  quantitative. 
The  more  usual  yields  lay  between  88  and  9i5yo  xiowever  because 
the  above  runs  were  made  on  especially  purified  reagents.  Evai 
9 0;i  is  a nignly  satisiactory  yielu  nowever  wnen  the  isolation  of 
the  Ketazine  is  avoiueu  entirclj. 


' f . 


V 


i,  — * 


i\ 


vi 


(M  y|’ 


. - -■  d/. 


i(i 


;T* 

• '4  i 


!'  *’j 

* »i 


CjPAt.'  '.■  ■ 

/ 


- - 

Wnen  poisoning  of  Lue  catalj'Si-  does  occur, as  shown  oy 
the  phenomena  descriuea  previously,  the  poisoning  , if  it  is 
slight. , may  oi ten  te  overcome  by  une  use  of  an  excess  of  catalyst. 
If  the  poisoning  oe  severe  Lhou^u  it  is  eest  to  recover  the 
iiyarazine  as  urocnloriae  and  as  much  of  tixe  acetone  as  possible 
and  stare-  out  on  a new  run.  The  origin  of  the  poison  is  often 
very  difficult  to  locate,  in  fact,  in  many  cases  subsequent  runs 
with  the  same  reagents  prove  to  be  normal.  In  a number  of  cases 
wnere  txie  catalyst  lost  ius  acLiviuy  more  ana  more,  apparently 
tiirough  exiiaustion  of  its  catalytic  acti  vi ty_^  wiiatever  tnat  may 
be  uue  to,  attempts  were  made  to  revive  tne  catalyst  by  shaking 
it  in  contact  witxi  air  for  varying  perious  of  time.  Even  on 
sxiaxing  for  as  long  as  two  xiours  no  revival  of  activity  could  be 
detected  in  any  case. 

IbOLATIOh  OF  IKB  REDuCiIOK  PROhoCrSo-  Wnen  the  theoretical 
amount  of  iiydrogen  has  ueen  acsorued,  the  valve  1 is  again  closed 
so  as  to  save  the  gas  in  tfie  tank  for  future  runs  and  to  avoid 
the  preliminary  evacuation  of  tne  tank.  The  flask  is  disconnected 
from  the  system  ana  allowed  to  stand  for  a fev^  minutes.  If  the 
colloid  is  still  homogenous,  and  equal  volume  of  acetone  is  added 
to  the  mixture  and  tue  contents  ^ i the  flask  shaken  violently  for 
a few  minutes.  The  colloidal  soiUbion  will  now  usually  be  broken 
up  into  large  flakes  which  soon  settle  out,  leaving  the  rest  of 
tiie  mixture  clear.  In  many  cases  tne  colloia  is  found  to  nave 
broken  ao  n wnile* the  reaucoion  was  still  going  on.  In  such 
cases,  01  course,  no  aadi  .i  nal  acetone  is  adaed.  In  eit..er 
case  it  is  oest  to  let  tne  mixture  stana  overnight  w.ien  the  clear 


n <- 


t- 

cL 


t 

i 


•'.‘1 

f 


i: 


i; 


■■ 


i 


> A' 


■y 


: 0.; 


L'f  ■ 

t 


i,'  I 
I 


/ 1 


If?  / 


I' 


42 


liquid,  may  Lhen  be  poured  througii  a large  pleated  filter  in  a 
few  minutes  and  the  mass  tnat  nas  settled  out  will  urain  within 
an  hour  or  less  after  it  has  been  piaceu  on  tiie  x'iltero  If  an 
attempt  is  made  to  fiiber  the  mixture  immeaiatel;,  after  tue 
colloia  lias  been  broken  or  ii  suction  is  applied  in  an  attempt 
to  save  time  it  is  very  difficult  to  filter  at  all  as  tue  black 
mass  oi  flakes  cannot  be  filtered  unuer  such  conditions  witn  any 
uegree  of  satisfaction. 

To  isolate  tiie  reduction  proauct,  tue  solution  is  made 
acid  to  Congo  , unless  already  auiu..  In  case  acetone  was  used  to 
breau  the  colloidal  state,  the  acetone  is  how  recovered  tiirougu 
distillation.  Tue  remainder  oi  the  solution  is  evaporated  down 
in  vacuum  on  a steam  ba-.h.  As  tue  solution  becomes  more  and  more 
concentrated  fine  long  uairlike  needles  oi  tue  uyurochloride 
begin  to  crystallize  out  on  the  walls  of  the  flask.  If  some 
lots  of  pure  product  are  uesired,  the  residual  solution  is 
now  well  cooled  in  an  ice  bath  anu  the  mass  oi'  crystals  tuat 
separate  out  are  filtered  of  oy  suction.  Tue  filtrate  is  con- 
centrated further  in  vacuum  and  anotner  lot  of  pure  crystals 
obtained,  finally  tne  iiltrate  is  evaoprated  to  dryness  to  get 
the  remainder  of  tue  hydrochloride  since  it  is  very  soluble  in 
water.  If  no  special  batches  are  uesired  the  evaporation  is 
carried  to  dryness  in  tne  first  place  anu  the  time  consumed  in 
cooling  and  filtering  saveu. 

hkbOVuRY  Of  Tiik  Cal'ALMoT;-  To  recover  tiie  platinum  the  filter 
and  clacK  mass  of  precipitate  are  permitteu  to  ury  tuoroughly 
before  attempoing  to  work  witn  them.  The  ury  filter  is  burned 


■1" 


45 


over  a porcelain  disii.  To  keep  irom  cracking  tne  uisn,ik  is  uest 

LO  nolci  tne  liiLer  wiLu  a pair  oi  glass  roas  until  tne  ashes  crop 

ox'r  into  tue  clish.  me  asnes  ana  caroon  in  t^ie  uish  are  tuen 

careiully  scrapeu  into  a crucicle  ana  ignited  wiLh  a clast  lamp. 

liie  metal  is  nexL  dissolved  in  aqua  regia.  Tixe  first  solution  is 

evaporated  aown  on  a water  uatii,  water  adaed,  evaporateu  to  dry- 

and 

ness  again,  iiydrocnloric  acia  auaea,y<^evaporated  again.  This 
alternate  treatment  witii  water  and  witu  K^drochloric  aciu  is  re- 
peated until  tue  platinum  solution  nas  ceen  evapprat ed, three  ^ 

times  witu  the  acid.  Water  is  again  adaeu  and  the  final  evaporation 
carried  out  in  vacuum.  The  residue  odtainea  now  is  dissolved  in 
a few^  drops  of  water  ana  finally  uilutea  to  tiie  same  color  that 
the  original  solution  uad.  It  is  now  readj^  for  use  as  a catalyst 
in  reduction  runs.  Tiic  loss  per  recovery  is  small,  Out  when  the 
same  platinum  goes  through  dozens  of  runs  the  loss  geos  more  , 

and  mors  noticeaole. 

SfMvikThICmj  DIIdOPhOPYLwHfDhAZIh'E.-  Tne  hyurochloride  obtained 
on  evaporation  of  tue  reduction  mixture  is  recrystallized  a few  ; 
times  from  small  quantities  of  alcoiiol  or  from  acetone,  before 
liberating  the  base  in  case  anciiyses  are  to  be  run  on  the  sample 
obtaineu.  IT  ohe  uase  is  to  oe  useu  for  tne  preparation  of  ae- 
rivatives  the  puriiication  is  unnecessary,  in  either  case  the 
base  is  liberated  by  means  oi  very  concentralea  sodium  or 
potassium  uydroxide.  It  floats  as  a layer  of  yellow  oil.  x'his  is 
separatea  from  tiie  water  layer  and  the  latter  extracued  twice 
witii  ether.  The  oil  ana  etiier  extract  are  united  and  dried  for 
■ 


44 


at  least  24  hours  witn  fuseu  potassium  u^aroxiue.  Tiiis  re- 
moves most  01  the  waver.  Alter  the  alkali  u.r^'in^  is  complete, 

Lhe  mixture  is  pourea  oil  bue  pooassium  ujdroxiae  and  into 
anotner  tuoe.Tiie  odor  oh  Lhe  oxiuation  produc L is  easily  noteu 
along  with  tne  ammoniacal  ouor  ox  hue  case.  Tne  iinal  urying  is 
done  by  freshly  preparea  aluminium  amalgam  prepared  irom  clean 
pieces  of  aluminium  foil  ana  mercuric  unloride.  _ne  amalgam  is 
allowe::.  to  react  witn  the  base  for  a week  or  more,  during  this 
time  tiie  jeilovj  color  and  tne  azo  ouor  uisappear  as  tne  oxiaation 
prouucts  is  reauced  to  the  nydrazine  again.  This  face  makes 
aluminium  amalgam  far  superior  to  any  of  the  oxide  crying  agents 
sucii  as  barium  oxiae  and  calcium  oxide,  ine  same  result  - 
drying  and  reduction  - obtained  ver^-  much  more  rapidly  by  metal- 
lic sodium  but  it  is  more  uifficult  to  get  rid  of  the  slimy 
sodium  compounds  tha u are  formea  during  the  crying  and  reduction. 
At  the  ena  of  the  drying  period,  tiie  base  is  carefully  poured  off 
the  aluminium  hydroxide  and  unciianged  amalgam  and  distilled  from 
a small  distilling  ilask  thru  wnicn  cry  nitrogen  gas  nas  been 
passing  for  some  time,  to  urive  :.ut  all  oi  the  air,  Tiie  stream 
of  gas  is  kept  going  curing  tne  distillation.  When  the  tempera- 
ture reaches  124*^  tiie  xirst  reciever  is  removeu  ax  ter  tne  flame 
nas  seen  removed  to  prevent  loss  curing  the  cuange  ox  re- 
ceivers, nefore  heating  attain  tne  surf  am  of  nitrogen  is  sent 
througn  tne  nev;  reciever  for  acout  10  minutes  to  remove  all  air. 
On  again  heating- and  distilling  the  remainder  of  tne  base  it  is 
found  to  practically  all  come  over  between  124  and  125°  as  a 
mouile,  colorless  liquid  of  ammoniacal  ouor.  Titration  by  iodine 


- 45  - 

or  'oj  hj'uroCiiioric  acid  anows  Lnac  the  case  is  not  quite 

pure  (97-8/0  purity.).  To  obtain  a ver-  pure  sample  lor  deoermin- 
acion  ol  cue  various  pny sical  consianos,  une  last  trace  of  oxida- 
tion product  (azo  compound)  is  removed  uj  using  a small  aosoro- 

53 

tion  apparaLus  ol  tne  tppe  u.escriDeu  by  Noyes  aiad 

Alter  the  124-5°  Iraction  nas  been  collected  in  tuis  small  reciev- 
er  under  tne  usual  precautions,  the  dry  nitrogen  gas  is  allowed 
to  continue  bubbling  throw^ue  absorber  until  tiie  inu.ex  ol  reirac- 
tion  remains  constant  curing  15  minute  intervals.  There  is  some 
loss  ol  symmetrical  hyurazine  along  .vitn  the  azo  compound  tnat  is 
volatilizeu  , hut  the  loss  is  far  smaller  and  the  purity  greater 
than  by  any  otner  metuoa  tried.  Analysds,  by  ra.piu  iodine  titra- 
tions, showed  that  tue  purity  ol  tiie  base  is  ecout  99. 5;^,  "'o 
preserve  the  pure  product,  the  absorber  I3  errptied,  with  the  gas 
still  passing,  into  a small  nitrogen  iilleu  bulb  which  is  then 
rapiuly  seaieu  by  a blast  lamp.  Apparently  the  base  thus  collect- 
ed may  be  kept  indefinitely^ wnile  in  contact  with  air  it  is  im- 
mediately Qxiuizea  partially,  i^ven  in  viell  stoppered  tubes  the 
decomposition  is  consiuerable . 

Q ana 

The  pure  base  boils  at  124.5  at  751  mm  pressure  ^is  a 
colorless  mobile  liquid  with  an  ammoniacal  odor.  It  reduced 
ammoniacal  silver  nitraie,  aqueous  silver  nitrate,  and  lehling's 
solution  in  the  cold. 

The  inaex  ol  refraction  (Abbe  instrument.)  is  - 1.4125 

D 

The  density , found- by  picnometer,  is  D31/4  ....0,7712 


c - 


- 46  - 

ketnods  or  Anaiybis.-  The  most  oonvenienL  metixoas  of  analysis  of 

bii6  iree  nj-arazines , ana  tne  metnoas  mosL  commonly  used  in  this 

investigation,  are  volume  uric  metnoas.  loaine  tirations  accord- 

bO 

ing  to  tiie  meLhOv^  ox  otolle  are  especially  convenient  and 
accurate,  the  rea.Cbion.  proceeas  accoruing  to; 

C^hl6iM2  ^2  — ^ 2 HI , xiie  oxiaation  product  is 

tne  azo  compound^ identified  dj  ouor,  inuex  of  refracuion,  and 
soiling  point,  otolle  assumed  that  tne  use  of  nis  meuiiod  in  tne 
caae  of  primary  njdrazines  leaa  to  nj-drazo  derivatives.  In  view 
of  the  fact  tnat  in  the  present  wort;  the  iiyu.razo  compound  is 
titraLed  with  iodine  under  che  conuitions  emplo^ea  uy  Sbolle,  it 
is  far  more  prodadle  Lnat  the  reaction  in  tne  case  of  primary 
njurazines  proceeds  according  to; 

2RmI“Im2  + 2 Ig  ^ n-K  -v*  4 HI , which  is  uhe  normal  De- 

havior  oi'  primary  n^urazines  towards  mild  oxidizing  agents. 
Another  volumetric  metnoa  tnat  ^ives  good  results, -results  tiiat 
may  later  be  cnectea  oy  an  iouine  tiLrarion  on  the  same  sample, - 
consists  in  tiuraoion  oy  H /lO  nydrocnloric  acid  using  methyl  red 
aS  indicator. 

To  cnecic  one  results  odtainea  by  titrations^  coraDustion 
analyses  were  also  resorced  oo  and  proved  to  oe  very  troudle- 
some  au  first,  xne  compound, as  well  as  most  of  its  derivatives, 
is  very  easily  partially  Onidized,  out  some  of  one  prouuccs 
formea  in  tne  parcial  oxiaation  seem  to  ue  very  staule.  laej 
pass  over  tne  long  la^er  of  copper  oxide  without  cnange  unless 
Lne  oxiue  iias  seen  heatea  to  a pink  color,  Even  thexi  the  de- 
composibion  must  be  very  carex'ully  regulaoea  bO  prevent  pushing 


r 


- 47  - 

tiie  ^ases  over  Ghe  oxide  aL  too  rapid  a rate.  In  Liie  Dumas 
nitrogen  ue  terminations  Liie  results  were  always  uign  if  the 
decomposition  proceedeu  too  fast  xor  even  as  little  as  a min- 
uu-e  01  time.  On  tne  otner  hanu.,  caroon  ana  iijOrogen  determinations 
v;ere  always  low  unuer  tne  same  conuitions.  After  more  tiian 
twenty  failures  with  the  usual  comdustion  furnaces,  an  old  fur- 
nace was  remodelled  to  fit  the  special  conditions.  The  heavy 
iron  ^'OKes  supporting  ti^e  uom.bustion  tube  were  replaced  by  a 
40  inch  length  oi  angle  iron.  Tiie  extra  lengtii  of  bea  permitted 
the  use  of  an  extra  burner  outside  of  tne  end  supports,  thus 
making  tne  xurnace  auout  ^ incnes  longer  than  it  xi.ad  been.  The 
tiles  along  botn  sides  of  tne  bed  were  so  arranged  tliat  txie^ 
are  readily  remov^able  in  case  decomposition  tnreatens  to  be- 
come too  fast.  Six  inch  sections  of  asbestos  board  are  used  as 
a roof  I or  the  furnace.  By  removing  the  section  above  tlie 
sample  it  may  be  rapidly  cooled.  To  provide  lor  cases  in 
which  the  removal  oi  tiie  tiles  and  roof  sections  uoes  not  bring 
tne  decomposition  into  immediate  and  accurate  control,  ice  is 
Kept  available  so  tnat  on  an  instants  notice  a small  block  of 
ice  may  be  rubbed  along  the  lower  side  oi  one  ued.  This  radical 
cooling  was  found  necessary  on  m.any  occasKions.  The  tendency 
to  very  rapid  decomposition  is  ver^  pronounced  in  nearly  all 
of  the  compounds  studied.  With  tiie  furnace  as  uescribed  and 
witn  very  slow  and  carexul  uecomposi tion  tne  results  are  as 
reliable  and  accurate  as  tiiose  on  more  easily  burned  suuSuances. 
Altnough  tiie  use  oi  oxygen  during  the  decomposition  in  carbon 
ana  hydrogen  determinations  results  in  small  explosions,  one  of 
wnich  vias  severe  enough  to  wreck  the  comoustion  tube,  air  may  be 


- 4:6  - 

safely  used  to  provide  for  a constant  and  even  movemenL  of  ciie 
gaseoufc)  aecomposi Lion  prouucus. 

Anal y ses*  OalculaLeci  xor  f Gjd<i»OBj  Hjl3«80j  I'jj24»  14^ 

I'ound;  G = 62. 3y;  62,17;  H=  15.97,14.31;  z 24 . 50 , 24 . 54^b 

An  afLempL  v\/as  made  lo  use  Lue  Kjeiiida.xil  rnethou  for  the 
nitrogen  ueLerminations , out  'che  usual  metnou,  of  course,  fails 
enLireiy  since  tne  nivrogen  is  all  given  off  us  free  nirrogexi. 
li  an  attempt  is  made  lo  reauce  the  compound  to  de  analyzed  bt 
the  hjenldahl  metnod,  the  aisappoinLlng  fact  is  revealed  that  the 
substances  do  not  seem  to  be  reducible  uy  any  ordinary  means, 

A large  number  oi  attempus  were  maae  to  reduce  the  hydrazo 
compound  to  one  primary  or  possibly  secondary  amine,  uut  no 
rnethou  tried  gave  any  sign  of  a reuuction  to  the  amine.  This  great 
stability  Lowards  reducing  agents  explains  tne  failure  of  the 
hjehldaiil  method  for  Lnese  compounds, 

A wet  metnod  for  the  determination  oi  the  per  cent  of 
nitrogen  in  Lnese  compounds  was  worxed  out  in  the  course  oi  this 
investigaoion . Except,  for  sligiiL  mouii ications  to  fit  1l  to 
special  conditions,  the  metnou  and  Lne  apparatus  useu  is  similar 
LO  a number  of  sucn  meLiiOds  developed  in  the  past.  A bulu  of 
about  2b  c.c.  capacity  is  blown  at  tne  uottom  of  an  ordinary 
LesL  oLiue , if  no  xlask  ol  sucii  snape  is  available  in  stock.  A 
one  hole  rubber  stopper  fiLs  into  tne  neck  of  the  flask,  A small 
dropping  funnel  is  sealed  into  an  B mm  piece  of  tubing  in  such  a 
W0.y  that  the  tip'of  the  dropping  funnel  stem  projects  well  down 
into  Lhe  flasK  wnen  the  b mm  tuuing  is  passed  just  through  a 
iiOle  in  Lixe  rubber  stopper  fiLLing  into  the  neck  of  the  de- 


49 


composition  flask. Above  tixe  ring  seal  a siiort  sideoute  is  sealed 
on  the  stem  of  tne  dropping  runnel. fhis  siueneck  is  the  opening 
Lhrough  wnich  carbon  dioxide  ^as  enters  the  apparatus  to  sweep 
out  tne  air.  between  the  ring  seal  and  the  rubber  stopper,  a 
sideneck  is  sealeu.  to  the  8 mm  tuoing.  This  opening  server  as 
outleL  for  Lne  decomposition  prouucts  and  for  tne  carbon  dioxido 
useu  in  rinsing  tne  decomposiLion  flask. 

To  determine  tue  per  cent  of  Nitrogen  contained  in  an  un- 
known substance,  tne  sample  is  weigned  into  the  decomposition 
flask  and  about  10  c.c.  of  waLer  added  to  it.  The  stream  of 
carbon  dioxide  gas  from  a ..ipp  generator  is  then  started.  After 
about  10  m.inuues  the  bubbles  of  ^as  will  ce  i ound  to  practically 
uisappear  wnen  passed  into  an  azoLometer  wnich  ib  filled  wiLh  a 
50/i  solution  of  potassium  nyuroxiae.  The  carbon  dioxide  is  then 
shut  off  and  Lhe  oxidizing  mixture  addeu  thraugh  the  dropping 
funnel.  As  oxidizing  fluid  a mixture  of  sulphuric  acid  and 

potassium  diciiromate  is  useu  in  mos'c  cases.  Just  as  effective 
as  this  soluLion  nov/ever  is  a mixLure  of  40^b  sulpnuric  acid  and 
potassium  permanganate . in  eitner  case  Lhe  mixture  is  added  drop 
by  drop  to  prevent  loo  violenL  decomposLion  of  Liie  compound. 

AfLer  the  mixture  iias  been  added  tne  bulb  of  the  dc;Comiposi tion 
flask  is  carefully  ueaLed  to  aoout  80^  unless  this  temperature 
is  reached  spontaneously  during  tne  oxidation,  finally  carbon 

A 

dioxide  is  ^sed  Lhrough  Lhe  system  again  until  the  volume  of 
nitrogen  in  tne  azoLometer  no  longer  increases.  Ail  other  sLeps 
are  similar  lo  tnose  employed  in  Liie  regular  Dumas  nitrogen 
determination, -he  metnod  is  noL  applicaule  lo  substances  that  do 


' t '» u , 

■ r rt^‘- 


• li 
» ■ ■• 


4 


i .; . i 


•■  ' i 


f 


r 


I 


1 - ' fi'l 


r,l/  r . ' 

I 


re 


4k 


^ a 


- 50  - 

not  give  oTi  the  nitrogen  reaaily.  Heating  to  too  nigh  a temper- 
ature causes  nigii  results  since  gases  tnat  are  not  aosorbea  by 
potassium  Hj-aroxicie  are  liueraLed  on  boiling  tne  solution. 

If  tne  substance  is  a liquid,  it  musL,  oi  course,  be  sealea  in 
a small  bulb  as  in  the  jjumas  luetnod. 

In  tne  case  oi  the  njurochloriue  of  s^-mmetrical  diisopro- 
pyl-h^drasine , fairly  close  results  are  obtaineu  on  using  Mohr's 
metnou  in  the  iialogen  determinations.  The  prim.arj  isopropyl-hydra- 
zine can  not  be  used  in  tne  presence  of  potassium  chromate 
since  tne  latter  is  immedia-tely  reduced  by  tne  base. 
bSHIVAilVIIn  Ur  Sx%kiix*.lU/*L  DI InOFROP >ffhwh'fDnAZIh2, - The  neutral 
hyurocnloride  of  tnis  nyurazine  is  outaineu  as  outlinea  in  the 
isolation  oi  tne  reauction  prouucts.  -ne  crude  salt  is  recrystal- 
lizeu  3-4  Limes  from  very  small  amounts  of  alconol  to  wnich  etner 
may  be  adueu  to  complete  tne  precipitation  oi  the  salt,  Otner 
recry stall! zing  agents  tnat  give  good  results  are  acetone  ana 
etnyl  acetate.  TTie  salt  is  very  soluule  in  water,  and  alcohol; 
insoluble  in  ether  and  in  petrolic  ether;  and  slightly  soluble 
in  all  otner  comm.on  solvents.  The  ny urocnloride  is  non-hygroscop- 
ic  and  has  markea  crystallizing  properties,  sometimes  arranging 
in  long  hairlike  needles  that  twine  along  tiie  sides  of  the 
container  for  several  Incnes.  The  substance  melts  at  198. 5°( corr . ) 
Conductivity  determinations  revealeti  tiie  ract  tnat,  at  nigh 
dilutions,  tne  hydrociiloride  is  appreciably  hyarolyzed.  since  the 
nyarazine  is  only  as  strong  a case  as  nyurazine  itself,  this  be- 
havior of  tne  nyurociiloriue  is  not  unexpected. 


51 


j^ji3.1  j'SOS#  oS-IcllIs-X/Gcl  iy*o5j  01^  ^ ^ 

rOunu.-  Gl,(Carius)  22,99;  (iviOhr' s)  25. 77 ; 23. 75; 23. 78;  23. 69)i 
N,  (uumas)  18.21j'i  ; (Vyet  keLuoa)  , 18.15;6 
liie  remaris.aule  results  ouoainea  with  kohr's  metnou  are  interest- 
ing, since  three  diiferent,  indepenuently  standardizeu  silver 
nitrate  solutions  were  used  ana  yet  the  results  are  all  unii'ormly 
iiign  in  spite  oi  tne  fact  txial  the  samples  analyzed  were  also 
entirely  different  ones. 

PKlil'J  YLTiilOSEivilOxttliJiiZIljE  Of  8YiViMhxri.lC^iL  DIiSOPrtO?yL“hy^PatZIi\iS, - 
ixiis  derivative  is  preparea  liy  aading  1.25  mols  of  pxxenylmustard 
oil  to  1 mol  of  txxe  free  hjurazine.  ro  avoid  overxieating  , the 
mixture  is  cooled  until  tixe  reaction  slo  is  doun.  a good  yield 

of  a yellowiSii  crystalline  precipitate  is  Obtained.  ohS  cTerlva- 
uive  putidied  for  analysis  by  recrystallization  from  absolute 

alcohol  or  irom  acetone,  fxxe  corrected  melting  point  of  tne 

0 

pure  substance  is  129.4  , It  is  insolucle  in  water, but  fairly 
soluule  in  txxe  otxier  common  solvents. 

Analyses.-  dalculated  for  G.  ,:-K  N,,b,  N rl6.747o;  S = 12. 75;^, 

found;  3,  (Garius)  12.45;  12.45.  N,(  Dumas),  16.73;b 
DEKZO^L  DERIVATIVE.-  A num.ber  of  attempts  to  prepare  the  benzoyl 
derivative  of  tixe  symmetrical  xiyurazine  failed  because  the  pro- 
duct was  always  a smear  wnicn  could  not  be  obtained  in  a satis- 
factory crystalline  state.  The  3cho Lten-nauman  metnod  and 
variations,  as  well  as  the  franzen  metnod,  using  a benzene  sol- 
ution of  tixe  base  instead  Ox  an  alxaline  solution  is  preparing 
the  derivative,  were  tried  during  txxis  work. 
oEIvIIGAR-'jAZI DS  Of  of ivilvin'i'-LiOAL  DllnOf  RO?lj_i-KlDi:.AZIx'iiE,  - lixis 


f 


52 


aerivat-ive  is  very  reauily  preparea,  aiificult  lo  purify  ior 
analysis.  1 mol  of  bhe  hydrociiloriae  of  tne  base  is  dissolved 
in  a little  v;ater  to  produce  a saturated  solution.  lO  Lliis  mix- 
ture is  aadea  a mol  of  potassium  emanate.  After  a few  minutes 
tne  mixture  sudaenly  v«arms  up  to  about  40*^  and  a half  crystalline 
half  oily  mass  lises  to  the  surface.  On  cooling  the  whole  turns 
crystalline.  Kecrystallization,  in  turn,  irom  uot  alconol,  from 
etner  ana  petrolic  ether,  irorn  alcohol  and  peLrolic  etner,  and 
from  eLnyl  acecate,  finally  prouuces  a prouuct  that  melts  at 
100°!^  corr . } . lurther  iieating  to  as  iiigh  as  225^  produces  no 
cnange  in  Lixe  melted  substance.  11  not  purixlea  by  the  number  of 
different  cecrystallizations  described  above,  the  melting  point 
of  the  substance  is  unsharp  usually  beginning  at  65^  and  finally 
melting  at  85-90*^. 

Analyses.-  ualculated  f.^r  Nr  26.41/o 

hound,  N = 26.26;^  and  26,lb/o. 

OXALiis-TE.-  The  oxallate  is  the  most  ueautiiul  and  tiie  most  easily 

prepared  salt  of  tne  hydrazo  compound,  but,  at  the  same  time,  the 

most  difficult  to  obtain  in  the  pure  stale,  free  base,  liberated 

as  usual,  is  mixed  with  10  volumes  of  dry  ether  and  anhydrous 

oxaliic  acid  acia  auueu  slowly  until  1.2  mol  of  uhe  acid  has 

been  aduea  to  tv/o  mols  of  tne  base.  The  wnole  mixture  is  a mass 

of  snow  wnite  crystals  as  tne  precipitate  lorms  immediately  and 

is  ratner  voluminous,  final  puriiication  is  accomplished  by 

six  or  more  recrystallizationx.  from  alcohol  followed  by  drying 

51 

at  100°  for  2 nours  in  a gtoren  drying  tuue  evacuated  by  a good 
water  pump.  The  salt  tnus  puriiiea  and  dried  melts  at  200°  and 
appears  to  ue  penectly  pure,  altnougn  the  cruue  product  is 


..  M 4 

0 ' " 
4 


I 


u 


I 


)■ 

,1 


» 

t 


i 


II 


I 


I 


I 


A • ' t • 


( 


'Jl 


,?)  'J : 


( 


if 


I 


Q 


t'' 


I 


I 


( 


- 53  - 

composed  or  a mixLure  o±  suostances  InaL  nave  ver^  nearly  tlie 
same  properties. 

Analysis.-  calculated  lor  N r IV. 39^ 

pound  .-  Wet  method.  Sulphuric  acid-  potassium  dichromate 
mixture,  heateu  to  hoillng.  N = 27.4;^  Alter  4 passages  over 
hot  copper  oxide  the  apparent  per  cent,  of  nitrogen  decreased  to 

20;6.  I 

II  Wet  meLnod,  same  oxiuation  method,  Out  no  external  heating. 
N = 17.43> 

III.  Same  metiiod.  Same  proceuure . 


K = 17.51/0 


Tne  analyses  snovi/  Lhat 


tne 
¥ 


salL  has  the 


® 6o 

6o 


.on.. 

^ o 


dilr- 

o 


formula; 


GH^  u GH5 

GH-::  H GKi: 

o o 

AGTlOh  Or  ALKiL  HALIDES.-  Among  derivatives  that  were  m.ade  only 
as  test  tube  trials  is  the  metnyl  iodide  derivative.  On  heating 
a mixture  of  meth^'l  iodide,  and  the  free  dry  base  slightly  the 
tvi/o  react,  with  consiuerable  evolution  of  heat,  to  form  a mass 
of  white  cr jScals.The  composition  oi  this  derivatives  nas  not 
been  SLuuiea.  I L is  very  soluble  in  water  ana  in  alcohol. 

Isopropyl  iodide  or  bromide  refuse  lo  reacL  with  the  iree 
base  unuer  ail  conuiLions  tried.  Sven  wnen  a mixture  of  .i-propyl 
alcohol,  dry  base,  ana  isopropyl  bromide  a^e  heateu, in  a closed 


tube  to  110^  for  tnree  nours  no  sign  01  a reaccion  product 


be  de Lee fed. 


t 


I 

' I' 


w' 


1 


I 


I 


1 

I 

> 


fj-j'-iw  ,iOUC 


I 


04 


iviOiMU-i\i  I TROSO  Diijiil  VAj- I VR  Oi-'  oi^IvUvifJTRloiAj  j^ilSuPrvOPYi-  xi^iJiLAZli'lR , - 

Early  in  Liie  wortc  wilu  Ine  n^urazo  compound  Llie  reaction 
of  nitrouB  aciu  on  tue  uo.se  was  shown  to  proauce  a straw  colored 
light  oil,  tnat  was  oDtained  in  variable  ^ield  under  tne  con- 
ditions then  selected.  The  product  uecomposed  within  a few  hours 
and  the  compound  was  left  lor  future  stud^. 

Wnen  the  stua^  of  tue  derivative  was  taken  up  systematically 
two  metnods  of  preparation  were  developeu. 
i*lrst  Metnod  Twenty  grams  of  th ; nyurocuioride  of  the 
symmetrical  ny urazine  are  uissolveu  in  the  least  amount  of  water 
tnat  -ill  just  dissolve  the  salt  at  room  temperature.  To  this 
solution,  15  c.c.  of  alcoriol  are  addeu  and  tne  resulting  mixture 
cooleu  by  a freezing  mixture  and  vigorously  stirred  by  a motor 
stirrer.  When  tiiorougniy  cold  a saturated  aqueous  solution  of 
25  g of  soaium  nitrite  is  aaaea,  and  tuen,  arop  by  drop,  15  c.c. 
oi  glacial  acetic  acid. 


ii  thiCK  la^er  of  oil  separates  out  as 


the  reaction  pro- 


ceeds. When  ail  of  tne  acetic  aciu  has  been  added  the  super- 
natant layer  of  yellow  oil  is  separated  from  the  lower  layer. The 
mixture  of  salts  and  water  is  tuen  extracted  repeatedly  witii 
ether  and  tne  ether  solution  adaed  to  the  separated  oil.  The 
final  volume  of  tne  etner  mixture  should  not  exceed  100  c.c. 

This  solution  contains  , ac>  tue  most  troublesome  impurity  a 
considerable  amount  of  ucetic  acid.  To  remove  the  acid  a few 
cc  Oj.  wauer  are  addeu  to  tne  euner  excracc  and  che  acid  neutral- 
ized by  means  of  souium  carbonate.  After  again  separating  the 
nitroso  compound  from  txie  lower  layer,  tne  lormer  is  now  dried 
for  about  15  minutes  witu  lumps  of  fuseu  calcium  chloride. 


1 


•W 


'V 


\ 


4 b ! V- 


♦:*.'»  Oiu’  ., 

I 

«*}U  : . U4J^ 

ktf  ■ 

I >■  '<'  %t  , 

' ■ ' ./.  ; 

*• 

^ - i tr 


VO 


I 


aL  biie  ena  Oj.  I'linubes  tue  calcium  cuioriae  is  replaced  bj 
i'resn  lumps  wnicn  are  allowed  to  stay  in  contact  witn  the  ether 
extract  for  1-2  hours.  The  liquiu  is  then  poured  off  and  is 
reauy  for  the  final  drying. 

Second  Method.-  Txie  second  methou  of  preparing  the  nitroso  de- 
rivafive  consists  in  thoroughly  mixing  molecular  amounts  Oi 
ury  souium  nitrite  and  dry  hydrochloride  oi  tue  hydrazo  compound, 
To  the  well  rnixeu  po’-'aer,  water  is  adaeu  undil  a thin  paste  is 
formed,  rhis  paste  is  then  warraea  in  a water  batn  to  70  degrees 
ana  kept  at  tnat  teraperaLure  for  1-1,5  iiours.  Although  tnere  is 
no  noticeaule  reaction  oe tween  the  nltrice  and  the  hydrociiloride 
at  room  temperature,  tue  reaction  proceeas  smootly  at  70'^.  If 
the  temperature  is  raiseu  to  80-00*^  the  product  is  uiscoloreu 
and  the  yielu  materially  decreased  due  to  decomposition.  In 
tlie  case  oi  tne  product  outaineu  oy  txie  lirst  method  heating 
to  as  much  as  40^  during  txie  period  wuen  gas  is  li aerated  in 
tne  solution  txie  whole  lot  oi  the  product  suddenly  decomposes  ; 
with  evolution  oi  neat  and  white  iumes.  This  behavior  has  not  j 
been  oDserveu  in  case  of  the  more  stable  product  obtained  by 
tne  second  method.  Tne  layer  of  yellow  oil  is  separated  and 
tne  lower  layer  extracted  with  etuer  as  in  case  of  the  first 
raetiiod.  Tne  etner  solution  is  not  drieu  with  calcium  chloride 
hovxever,  but  is  cooleu  in  a Ireezing  mixture  to  remove  ..s  much 
of  t.iS  i. -lOiiano'Sd  n^ULrociiioride  as  possible,  :iiis  is  the  main 
impurity  obtained  by  tne  seconu  metnod,  and  is  reauily  removed 
on  distillation.  The  yielu  is  not  quite  as  good  (60-65/0  instead 
of  60-70/O  in  case  of  lirst  metnod)  as  tnat  obtained  by  tne 


first  metnod 


I 

'j 


[»  i 


. “ .A  a.  v'lr*; 

' ■ 'i 

■ 'A. s Jj6iJ'00)!  •’ 

T“ 

. ^‘1  -'i',:'  .,-.  ij>z^ 


56 


The  treatment  of  Lae  nitroso  derivative  obtained  by  the 
Lwo  methods  is  identical  alter  tne  calcium  chloride  treatment 
01  the  product  obtained  by  the  first  metnod  and  the  removal 
of  the  uncii‘'nged  h^'urochloriae  found  in  the  product  oi  tiie 
second  metaoa.  iaej^L/ier  exLract  is  dried  over  night  over  an- 
hyarous  soaium  sulphate  and  kept  cool, in  tiie  meantime,  in  an 
ice  box.  Tne  decomposition  oi  Lae  small  amouno  oi  di-nitroso 
compound  LaaL  seems  to  be  formed  by  tne  lirst  metnod  snould 
be  complete  uy  next  morning.  The  ice  cooling  is  then  dis- 
continued, cut  tae  extract  leit  in  contact  witn  the  sodium 
sulphate  ior  3-4  aays  longer.  ’Waen  tae  liquid  is  then  carefully 
pourea  off  the  soaium  sulpaate  and  distilled  in  vacuum  the  etner 
is  readily  removed  witnout  exoernal  ixeating,  although  time  is 
saveu  by  aeating  tne  solution  to  25°  by  a water  oath  during 
tiiis  part  of  tne  distillation.  As  soon  as  all  of  the  etner  is 
removed,  tne  yellow  residual  oil  is  distilled  under  a higher 

vacuum.  At  6-8  mm  the  main  protion  oi  the  liquid  distills  over 

On 

between  64  and  66  . On  reaistiallat ion  about  9dfo  of  the  oil 
comes  over  between  65  and  66°  at  7-8  mm  pressure, 

Txiis  pure  product  has  a ueep  straw  color,  a peculiar 
sweetish  odor,  anu  is  now  stable  at  room  temperature.  Attempts 
to  distill  tne  oil  at  atmospheric  pressure  siiowed  that  this  is 
impr au ticaole  since  decomposition  starts  at  aoout  150°  and  at 
tne  apparent  boiling  point  of  16u-2°  the  nitroso  uompound  de- 
composes ratner  rapidly  with  evoluuion  of  wni ce  fumes.  The  yield 
of  crude  product  could  not  well  ue  determined  anu  that  oi  tne 
pure  oil  is  variaole  since  tne  losses  during  drying  and 
distillation  are  variable,  on  normal  runs  the  jielu  of  pure 


II 

( 


I 


1 

II 

I 


II 


‘i 

I 

f 


• -‘in / . f-.o 

^ 1'-  f 


f 


- b7  - 

nitroso  derivative  ranged  Irom  60  to  an  occasJiional  70^^  or 
the  calculated  jlela.  The  product  is  iairly  soluble  in  water, 
slightly  soluble  in  benzene  and  in  petrolic  ether,  and  readily 
soluble  in  alcoiiol,  ethyl  acetate,  and  eLher.  Tiie  derivative 
gives  tue  Lieosrman  reaction,  and  shows  otuer  properties  or  . 
nitroso  compounds.  Ii  a arop  of  ferric  chloride  is  added  to  an 
aqueous  solurion  ol  a lew  drops  ol  tne  derivative  a blue-violet 
color  is  proaucea,  in  case  oi  an  alcoholic  solution  ferric  chlor- 
ide proQuces  a green  color,  while  a solution  in  chlorof orm( or 
even  tne  diluce  solution  in  oenzene  ) shows  a reu  coioracion. 
Analyses:  dalculatea  for  , h = 2b.96;tJC=  49 . 65  j H=10. 

found;  C , 49.65,  49.39;oJ  h,  10.43,  10.22)bJ  N , 28.66,  28,20/o 

= 1.4420  D 22/4  = .9440 

oODIUm  salt  Of  THE  i\iITK0S0  HiDhAZIbE.-  If  the  nitroso  compound 
made,  preferably,  by  tiie  seconu  metnod  is  diluted  with  ether 
and  then  treated  wicn  a sauurabed  soiuLion  of  sodium  hydroxide 
in  alcohol,  the  whole  soluuion  Lyrns  to  a mass  of  very  fine 
crystals  aiter  standing  for  a few  nours.  the  same  result  is 
outaineu  wnen  soaium  metriyiaue  or  ethylate  is  used  insteau  of 
tne  saturateu  alcoholic  solution  of  rne  hydroxide.  The  mass  of 
needles  is  lilterea  oif  oy  suCLion,  wasxieu  with  ether  and  dried 
for  2-3  hours  in  a vacuum  dessicator  before  tne  analysis  is 
attempted.  Since  no  solvent  was  i'ouiid  from  wnich  tne  salt  could 
ce  recrystallized,  tne  analytical  results  are  only  approximate, 
but  suificienciy  close  to  leave  no  douct  as  to  the  corapuund  ob- 
taineu. 


e 


< 


P6f!c 

U'C  - 


I 


i. 


. :C‘.  : ■. 

? 


il/ 


. M . ' 


t 


I 

■i 

- 

;f; 


- 5b  - 

tlnalj'ses;  baicuiatea  lor  Gj.K-|_^i\i;^Ul'}a,  Na  r 13. 77^^;  N,=  ki6.15/o 
I'ounu.;  Na  = ; i4.54;^(?  J N - 23.97;^o 

Tiie  sodium  was  u.eLermined  aja  tne  suipiiaoe. 

A peculiar  reacLion  Lnat  was  always  observed  wnen  the 
nitroso  derivative  was  neateu  in  tiie  presence  oi  alkali  or  when 
iL  stooQ  in  contact  witxi  Lne  alnali  lor  longer  periods  or  time, 
is  rue  lormarion  o±  a small  amount  ol  an  isonicrile.  An  extort 
was  made  ro  isolate  ruis  prouuct^ uut  uue  ^iela  is  too  small  to 
isolate  or  uerect  the  carbylarnine  except  by  its  odor.  It  would 
thus  ue  impracticable  ro  prepare  enougii  of  the  nitroso  compound 
Lo  be  able  to  iuentiiy  tue  isonitrile  obrained  from  it. 

A number  of  attempts  were  made  to  reduce  the  nitroso 
compound  to  oxie  con  ssponding  amine,  but,  as  is  usually  rhe 
case  wnen  rnis  type  of  nitroso  compounu  is  reducea,  the  only  re- 
ducLion  proaucts  rnab  could  oe  isolaceu  were  ammonia  and  the 
ori^jinal  hyurazo  compound.  Attempts  to  afiect  tne  reauction  by 
means  of  catalysis  failed,  apparently  because  tne  plarinum 
catalyst  is  immediately  poisoned  uy  braces  ox  free  nitrous  acid 
present,  lu  was  uopea  Ixxal  reduction  of  txie  souium  salt  by  means 
of  Liie  cataljbic  mernou  would  ue  a success,  but  only  4-5;^  of  tiie 

theoretical  amount  of  n^urogen  gas  was  auosrued. 

CH^  ^dii^ 

2 .2  ' -Azobispropane , uK-N::N-chi  .-  Twenty  grams  of  dry  hydro- 
chloride  of  tne  symmeLrical  nyarazine  are  treated  witn  a 50)i 
excess  of  ury  po-wuered  copper  oxiue.  The  substances  are  then 
thoroughly  mixed  by  suaking  tne  ilask  in  which  the  reaction  is 
allowed  to  lake  place.  After  about  15  minutes  a peculiar  sweet- 


' J.  . < v 


fe  ••  \ 


o.".'.:f; 

'■>1 

!ie  oi; 


■'  -I 


- 59  - 

isii  odor  becomes  noticeable,  aixer  an  iiour  or  two  a crace  of  mois- 
ture may  be  noLiced  on  some  ox  tne  crystals,  next  morning  the 
WiiOle  mass  is  aisLincoiy  moist  and  Liie  ouor  of  tne  oxiaation  pro- 
auct  is  mucn  more  marxed.  After  2-o  nays  tne  mass  is  so  wet  tnat 
it  may  be  poured  out  ol  tne  reaction  xiask  as  a tnick  paste.  Alter 
several  days  more,  one  reaction  may  be  consiaerea  complete  and 
Lne  xiask  is  connecLed  to  a condenser  und  heated  gradually  in  a 
water  batn.  li  tne  temperature  is  raiseu  gradually,  tne  large 
cubical  ruu,/y  red  crystals  of.  an  unstable  copper  salt,  observed 
on  tne  walls  of  one  flask  witiiih  o6  hours  ax  oer  the  oxidation 
mixture  was  made  up, suddenly  change  from  reu  to  greenish  white 
while,  at  the  same  time,  at  88.5^,  tne  oxidation  product  begins  to 
distil  over  as  ligbt,  straw  colored  oil  vjith  a nausea oingl^ 
sweet  and  very  cxiaracteriztic  odor  — an  odor  tnat  may  be  used  as 
a ver^'  sensitive  test  for  the  hyurazo  compound  or  its  nydrochloridf  . 
Tiie  fraction  distilling  over  between  92  and  98°  is  composed 
lar^^ely  of  water  wnich  forms  a separate  layer  at  tiie  bottom  of 
tiie  reciever,  Tiie  oil  is  readily  separated  irom  the  water  layer, 
the  latter  tnen  extracted  several  times  witn  etiier,and  the  mixture 
of  etner  extract  and  oily  layer  dried  for  24  iiours  over  fresh 
fused  calcium  cnloride.(Jn  reuistillation  tne  product  almost  all 
distills  over  beoween  88  and  89°  as  a mobile  liquid  witii  a 
faint  straw  color.  The  fact  tnat  the  same  intensity  of  color  is 
obtained  with  ever^'  sample,  snows  tnat  tne  color  is  not  uue  to 
some  trace  of  impurity',  tne  corrected  boiling  point  at  750  mm  is 
88.5°  at  which  temperature  over  90/o  of  the  oil  discills  over. 


“ 60 


Tne  pure  oxidation  product  is  neutral  lo  litmus,  is  insoluble 
in  acius  ana  uases,  and  miscible  wiLh  all  oi  the  common  organic 
solvents,  ho  derivabive  could  be  outaineu  witn  aqueous  hydro- 
cyanic acid,  wiun  pouassium  emanate,  witn  ororaine,  and  witn  oLher 
reagents  that  often  aua  on  Lo  uouble  uonds, 

Tlie  product  in  a 10  dm  tuoe  showed  no  aosorution  bands  in 
tiie  visiole  part  of  the  spectrum  wnen  examined  with  a good  spectro- 
scoije.  At  Lhe  extreme  vioiet  end  of  tne  visible  spectrum  a slight 
absorbtion  seemed  to  occur,  cut  no  attempt  was  made  to  determine 
whether  there  is  aosorbtion  in  the  ultraviolet  or  not,  since  suit- 
able apparatus  was  not  available  at  the  time. 

The  index  of  refraction  for  sodium  light  wnen  an  Abbe 

25 

ref ractom.eter  was  useu  'was  ^ : 1.5690.  On  a number  or  otner 

samples  of  the  pure  proauct  this  value  was  obtained  so  txiat  it  is 
the  most  accurate  value  determ.ined  on  an^  of  the  compounds. 

- .7408  as  determined  by  means  of  a modij.ied  Oprengel  pic- 
nometer. 

-.lie  yield  of  oxiuation  prouuct  from  20  g of  tiie  pure 
hydrochloride  is  21  cc  of  Liie  moist  and  19  cc  of  Lhe  pure  oil. 

The  calculatea  yicla  is  20  cc  so  tnat  tiie  yiela  obtained  is 
practically  quantitative. 

Tne  oxidation  product  is  oest  prepareu  by  tue  me Luod  de- 
scribee, cut  tnere  are  a numoer  oi  otner  methods  available  for  the 
preparation.  As  inaicateu  previcusly,  ioaine  titration  goes 
quantitatively  to*  tne  azo  compound.  Oxidation  by  means  or  any 
weak  oxidizing  agent  prouuces  ti^e  azo  compounu  altxiough  the 
yield  may  oe  poor.  Even  such  powerxul  oxidizing  agents  as 


■ . 


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61 


potassium  per^manganate  anu  pouassium  uiciiromaue  prouuoe  a small 
amount  oj.  azo  compound^  as  suov/n  oj  one  oaor • In  case  a small 
amo- nt  ox  one  oxioialion  proauc  o is  needea  on  short  notice  it  may 
oe  prepareu  witn  a :,iei^  of  60  Lo  70;t  oy  oxidizing  the  ease  by 
meoins  oi^lKaline  copper  salt  solution.  Copper  ace  Late  appears  to 
give  one  ueso  resuio.  xne  ny urocnloride  anu  copper  acetc^oe  are 
piacea  in  a aisoillin^  liask.  A uilute  solu..tion  ox  souium  nydroxiae 
is  oi.en  audeu  and  tne  contents  oi  trie  ilask  neateu.  on  a steam  bath. 
Tne  azo  compound  distills  over  as  in  case  ol  one  copper  oxiu.e- 
oxdiation  experiments  and  i is  puriiieu  as  in 

case  01  tiie  regular  metiiou. 


Analyses;  calculatea  for  C = 63.15p;  ri 

round  ; G = 65.18/c;;  63.3S/o;  63.02p:  H = 12.03  ; 

H a 24 • 67^  _ 

fv'iOlecular  '?jeight  uetermina oions;  (j^reezing  point 

Galculaoed  r 114  ; round  110  anu  119. 


- 12.28^;  K=24.56/o 
12.45;  12.46;y 

iov^eringjjyenzene ) 


neuuction  of  tne  Azo  Derivative;  Two  cubic  centimeters  of  azo 
compound  reduced  in  a small  reduction  apparatus,  absorbed  the 
calculatea  amount  of  nyurogen  in  less  txian  an  nour  unuer  tne  in- 
fluence of  colloidal  platinum  us  catalyso.  iteuucoion  with  sodium 
amalgam  or  witn  sodium  in  alcoxiol  yields  tne  same  produco,  one 
symmetrical  diisopropyl  Ujuiazine. 

H^.drolysis  of  Liie  Azo  oompounu  .-  me  azo  comp^una  aoes  not 
change  to  any  uppreciaole  extent  after  rexluxing  for  an  nour  with 
a 2%  solution  of  nyurocliloric  acid.  Alter  4 hour  of  rexluxing  with 
a 4 ^ solution  of  the  same  acid  no  change  could  oe  noted,  al oer 
4 iiours  of  refluxing  w'itii  a 10;b  solution  Ox  the  acid  Lnere  was 
a considersujle  aecrease  in  volume  of  the  iioating  la^er  oi  azo 


-'^  ' 

'■i'Ui 


.U9 


/ 


^ ^ I 


i : 


'4  i 


^<j 


' < ' 


1 


I 

i 

I 


< 


L 


- 62  - 

compound,  Dut , nL  tne  same  >rabe  of  n^urol^'sis  aL  least  3 nours 
more  would  nave  seen  requirea  to  complete  the  hyarolysis.  After 
one  hour  of  ireaLment  witii  a 20^3  solution  of  concentrated  acid  in 
water,  tne  oily  layer  naa  practically  all  oe  usea  up.  The  compound 
is  now  nydrolyzed  by  refluxing  with  a mixcure  of  1 part  of  concen- 
traceu  n^ arociiloric  acid  ana  1 pare  oi  wacer.  V/iUi  this  concencrat 
ea  solution  tne  layer  oi  oil  aisappeara  wiLhin  naif  an  nour  of 
reiluxing.  An  excra  half  nour  is  usually  used  to  be  sure  that  the 
hydroi^'sis  is  complete,  he  mixture  is  then  concentrated  in 
vacuum  until-  the  resulting  syrup  becomes  slightly  colore  a.  The 
hydrochloride  of  prima.r^-  isopropyl  hydrazine  cr^-stallizes  out  as 
small  white  needles  on  cooling  the  s^rup  in  a freezing  mixture. 

The  salt  is  iiltered  off  rapidly  and  o^ie  filtrate  concentrateu 
iurtner  until  again  st'rup^  .The  fhedzihgj.  out  and  concentration 
processes  are  '"e-oeateu.  until  Qni^  a verj  small  amount  or  resiuual 
solution  is  left,  rhe  small  amount  of  h^arociiloride  left  in  this 
is  precipitated  b^  means  of  a mixture  of  a few  drops  oi  alcohol 
and  about  5 c.c.  of  ether.  The  h^ arochloriae  maj'  then  be  purifieu 
ana  analyzed  or  the  ease  ma^'  be  liceratea  from  the  salt  and 
tue  dibenzoj/1  derivative  made  in  identiij'ing  this  n^-arol^sis  pro- 
duct . 

To  identify  acetone  - the  otner  iiyurolysis  product-  a second 
lo-t  of  azo  derivative  is  hydrolyzed  bj  a 10  % solution  of 
hydrochloric  acid.  This  does  not  cause  as  much  loss  Ox  acetone 
as  the  more  concentrated  solution  oi  acid  does.  After  the  hydroly- 
sis is  complete,  the  acetone  is  simply  distilled  off  and  iaenti- 
lieu  by  means  of  the  uenziliuine  compound,  by  tiie  iodoform  test. 


- 63  - 

and.  'Dj  tne  souium  ni  Lroprussiae  color  lest. 

Conversion  Lo  tlie  Hydra  zone IT  the  azo  compound  stands  lor  a week 
or  more  over  strong  alkali  or  if  it  is  heaueo.  for  a few  hours  au 
180*^  with  concentrated  potassium  njuroxide,in  a closeu.  Luije,Lhe 
azo  u6: ivative  is  partially  converbed  to  one  u”drazone  as  evidenceu 
bj'  tne  nydrazone  odor,  the  greaLly  changeu  index  oi  refraction, 
and  txie  boiling  point  of  lOO’ to  118 '’lor  tiie  resiuue  left  on  dis- 
tilling off  tne  unciiange^.  azo  compound.  Since  only  a small  amount 
could  be  obtained  in  a run  of  this  Kind  tne  n^'arazone  could  not 
be  analj'zeu  because  rhe  purificacion  of  such  a small  amount  of 
prcducu  is  too  uiificul'^.  Tue  iucc  LuaL  even  sucn  arastic  treac- 
ment  as  iieating  bo  180°  only  parxiaily  converbs  tne  azo  to  the 
iijuiazone  uerivuLive  snows  tnai  tne  azo  derivative  oi  symmetrical 
diisopropjl  iij-urazine  is  an  uncommonly  stable  compound.  All  at- 
tempts to  effect  the  reverse  rearrangement  - h^'drazone  to  azo- 
f ailed. 

Preparation  of  Di-isopropylj>’  in  tetra  substituted  liyarazines  =tnd 
in  a few  symmetrical  disubsti tubCn  nyura tines  oxidation  or  heat 
tenu  to  uecompose  tne  azo  compounds  to  produce  nitrogen  gas 
along  with  the  dialkyi  compouuu  produced  tnrougix  reuniting  of 
the  two  alkyl  rests,  in  spite  oi  a large  number  of  uifferent 
experimiOxits  carrieu  out  in  an  attempt  to  find  a practical  method 
of  uecomposing  the  azo  compound  obcaineu  in  tuis  worn  into  nitro- 
gen gas  and  di-isopropyl,  none  o±  the  metiiods  trieu  gave  more 
than  traces  df  paraffins.  . 


64 


PKSPAKii'i'luw  UF  iviUWU  ISO'^PrLUPYijhyjjKAZIi'^E. - Tile  primary  liyurazine 
majf'  be  prepared  oj  laree  dilierent  metiiods.  Two  of  tixese,  the 
hjdrolj'sis  01  tne  azo  aerivabive  and  oi  Lne  hj-drazone  are  similar 
and  nave  ueen  parbly  uescribea.  The  ujdrol^sis  ol  tixe  ixydrazone 
id  eifecteu  by  verj  dilute  acids,  even  water  iiyurolyzes  cnis 
compound,  so  tae  preparation  of  tiie  primary'  a^'urazine  from  Ixiis 
compound  is  exorern  ly  simple.  Vuietixer  produced  bj  hyarol^sis  of 
tne  hydrazone  or  of  2 , 2 ’ -azobispropane  the  ayarolysis  mixture  is 
concentrated  in  vacuo  as  describeu  before,  tne  iiydrocaloride  is 
isolateu,and  purifiea  uy  recrystallization, and  tlien  dbcompQsed  by 
means  of  concentrated  alkali. 

The  taird  ana  best  melixod  of  preparing  the  primary  hydrazine 
consists  in  the  catalytic  reauction  of  a mixture  of  1 mol  of 
pure  acetone,!  mol  oi  ayurazine  iiyarate,  and  1 mol  of  hydrochloric 
acid  in  exactly  tae  same  manner  tnau  tne  reduction  of  ketazine 
was  efiectea.  Tne  procedure  tarougiiout  is  the  same  except  that 
the  aydrocnloride  of  primary  isopropyl  ayarazine  decomposes  too 
easily  to  permit  tae  evaporation  to  uryness  of  tae  reduction 
mixture  even  in  vacuo.  Accordingly  i^ne  iiydrocaloride  is  isolated 
by  cooling  the  syrupy  solution  of  Lhe  hyarociiloride  in  a freez- 
ing mixture  to  freeze  out  as  m.ucii  as  possible  oi  the  salt  at  a 
time.  The  mass  ox  fine  needle-like  crystals  is  then  filtered  by 
suction.  The  xiltrate  is  concentrated  furtaer  and  the  freezing 
and  iiltcring  repeated  until  the  amount  of  syrup  leit  aoes  not 
exceed  b to  8 cc  wnen  the  rest  of  the  salt  is • precipitated  by 
m^eans  of  a little  alcoaol  ana  a large  excess  of  ether,  ny  waat- 
ever  one  of  tne  taree  metaods  mentioned,  the  salt  may  nave  been 


Ca-O. 

n 


1,. 


I i 

* 

■ ir* 

V ^ 

1«. 


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, t 


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f ‘<JW 


♦I  . . f 

■ • . ••  /Vi^ 

'•  ■'■'  • 

Tv  " 

•‘  '■  ■’■ 
* -'iv  -'jflJ.  'n, 

, ' 


^ m w wf 


- . Jf 


c 


- bb  - 

ODLcdned,  ine  isolation  ox'  tne  xij drocnioride  is  accomplisneu.  in 

exactly  tue  same  manner,  xne  arocnioride  ouLainea  tnrougn 

ujorol^sis  of  2,2 ’ -azoDispropane  by  50;b0  nydrocniorio  acid  is 

verj  hygroscopic, wnile  chose  obiaineu  irom  Lne  hyarazone  and 

iiom  the  reduction  of  the  acetone-liydrazinehyarate  mixture  are 

onl^-  verj  sligntly  hy groscopih  . The  h:,'groscopic  salt  was  not 

salt 

analyzed,  but  since  tne  non-hygroscopic^^roves , chrougii  analyses, 
to  oe  the  neutral  salt,  xuere  is  little  doubt  auout  the  identity 
of  the  hygroscopic  compound  , especially  since  both  hydrochlorides 
yield  the  same  base  on  treatment  witn  concentrateu  alkali,  so  that 
one  must  be  cue  acid  and  che  otuer  tue  neutral  salt  unless  tiiey  , 
be  tne  same  compound.  This  is  not  che  case , however , since  re- 
crystallization uoes  nox  ^ield  a non-hygroscopic  salt  melting  at 
114.6®. 

ISULnTION  OP  Phikhhx  ISOPnOP'^Lh'^DRuZINE,  • “ On  treat- 

ment  of  uhe  liyarocnloride  wicii  solid  sodium  or  potassium  hydroxide 
tiie  mono  isopropyl  hydrazine  is  lioerabed  as  an  oil  tnat,  in 
appearance  and  odor, is  very  similur  uo  tne  symmetrical  hydrazine 
describe^.,  previously.  The  base  cannot  , however,  oe  obtained  in 
a pure  state  by  any  metiiod  or  device  tried  so  far.  A constant  of 
tiny  cubbies,  usually  starxing  from  some  fine  dust  particle  or 
snarp  point,  is  cnfn'm.Miith---  given  off  for  an  indefinite  period  of 
time.  The  amount  oi  ^as  given  off  is  so  small  that  a very  large 
amount  of  proauct  or  a very  long  perioa  of  time  would  be  necessary 
to  collect  enough  tjSis  to  identity  it.  As  the  oxidation  of  primary 
hydrazines  results  in  tiie  elimination  of  nitrogen,  it  is  probable 
tnau  the  ^as  escaping  is  nitrogen  gas. 


- 66  - 

Tiie  accurate  determination  oj.  the  uensit^  is  made  irnpossiole  uy 

the  gas  evolution,  and  inueed  would  ue  of  little  value  on  a 

compound  tnaL  is  adaiittedly  not  pure.  Tne  index  of  reiraction 

snows  tnat  tue  nydrazine  gradually  decomposes.  The  purest  fresn 

base  examined  j^ave  a boiling  point  oi  106-7  at  748  mm  and  had 

2 

a density  of  .814  at  25  degrees.  ^ - 1.4280 

The  base  is  miscible  with  water,  alcohol,  acetone,  and  ethyl 

acetate,  but  only  slightly  soluble  in  ether  and  peLrolic  ether. 

Primary  isopropyl  ny arazine  is  a verj  strong  reducing 
agent,  in  tuis  respect  even  excelling  the  symmetrical  hydrazine. 
In  addition  to  reaucj.ng  silver  nitrate  solutions  and  rehling’s 
solution  in  tne  cold,  it  also  reduces  potassium  chromate  as  was 
snown  when  an  attempt  vvas  made  to  determine  the  chlorine  of 
the  hydrochloride  by  mea.ns  of  kohr’s  metuod. 

Iodine  Litracions  and  hjdrochloric  aciu  titra Lions  may 
be  useu  as  in  case  of  tne  symmetrical  hyarazine. 

In  3.S  much  as  Lne  case  is  known  to  be  impure,  no  attempt 
-xds  been  made  to  analyze  it.  To  prove  its  identity  conclusively 
the  iiydrochloride , the  plienyltuiosemicarbazide , and  the  di- 
benzoyl derivatives  were  prepared  and  analyzed. 
jJhRI  VATIVEb  OF  PKIiViAHi  ISOPROF Ynil^DKAZINE. - 

The  hydrochloride  nas  been  partially  described  in  con- 
necLion  with  tne  nydrolysis  of  the  azo  and  xiyurazone  derivatives 

(page  64-65)  The  crystals  isolated  from  the  residue  left  on 
concentration  or  the  hydrolysis  or  the  reduction  mixture,  are 
dissolved  in  a very  small  amount  of  alcohol.  After  heating  to 
dissolve  all  of  the  crystals  ether  is  adueu  to  the  solution 


I ' 


f; 


*1 


67 


until  Lhe  liiot  permanent  cloudiness  is  oblaineu.  On  cooling  unis 
solution  to  -lO^or  lower  oy  a good  freezing  mixture,  the  salt 
crystallizes  out.  Tiie  aiooliolic  filtrate  suouid  never  be  dis- 
caraea, however , since  the  hydroculoride  is  so  extremely  soluble 
that,  even  at  -10*^  much  more  stays  in  solution  than  is  frozen  out. 
Two  such  treatments  give  a product  that  is  sufficiently  pure  to 
De  analyzed.  Ethyl  acetate  may  be  used  as  a recry stall! zing  agent 
but  tue  hyarociiloride  is  only  very  sligiitly  soluble  in  etnyi 
acetate  and  large  amounts  of  the  solvent  must  be  useu  to  obtain 
a xair  sizeu  crop  of  crystals  on  freezing  the  solution. 

The  pure  nyarociiloride  is  non-liygroscopic(  i , e , if  we  are 
working  with  tiie  neuLral  salt)  melts  at  114.5°  (corr,),and 
is  verj  soluble  in  water  and  in  alcohol,  slightly  soluble  in 
chloroform, benzene , ethylacetate , and  acetone,  and  insoluule  in 
ether  and  petrolic  etner. 


Analyses; 


Qalcuiated  for  C H^  1^1,^11(111, 

o XU  ^ 


h z 2 5 , 54  ;!b 


found;  N z 25.39;6 

Pheny Ithio semi car bazide  of  primary  I sopropy 1-Hydrazine. - 
Wnen  a mol  of  pnenylmustard  oil  is  added  to  an  etner  solution  of 
1 mol  of  free  primary  isopropylnydrazine , fine  long  needles  of  the 
mustard  oil  derivative  precipitate  out  in  a few  minutes.  These  are 
recrystallized  from  alcohol  by  adding  water  or  ice  to  a hot 
solution  of  the  derivative  in  alconol,  'whien  the  first  permanent 
clouainess  appears  on  adding  water,  tne  solution  is  cooled  well 
w.ien  tne  derivative  precipiuates  out  in  good  yield,  fiie  melting 
point  of  tne  pure  uei  ivative  is  ^.41 , 5°(  Corr . ) . It  is  very  soluble 
in  hot  alcoxiol,  in  aceton.;,  chloroform,  and  etxiylaacetate , and 
insoluble  in  water > etner,  ana  petrolic  ether.  


N r 20.09^^ 


Analyses:  Calculated  1‘or  G Nr^S  , 

13  J-O  o 

Found.  (Dumas)  N z iy»B6  and  20.23/5. 

Di-uenzoyl  Derivative  of  Fnimar.y  Isoprop.yl-H.ydrazine . 

CH3 

^CH-NK-F^  Two  mols  oi'  benzoyl  ciiloride 

C1I3  ^“C,,n3 

0 ^ are  aaued  to  a concentrated  sol- 

ution of  tue  iiyarociiloride  in  waper.  Sodium  uarbonape,  in  excess 
is  aaue^  to  this.  After  a lew  minutes  of  lively  stirring  a react- 
ion occurs  with  evolution  of  consideraole  heat.  A-  first  no  pre- 
cipitate or  otiier-  product  can  ue  uetecced.  Ax  ter  stirring  and 
ruDbing  tne  smear  witn  sodium  carbonate  a few  minutes  the  deriv- 
ative sudaenly  crjStailizes  out,  Puriiication  is  accoraplisneu 
witn  alcouoi  and  vvater  in  exactly  uhe  same  manner  as  in  tne  case 
of  the  phenyl thiosernicarbazide  aerivative.  Tne  pure  product  con- 
sists of  beautiiul  white  needles  melting  at  161 . o'^(  corr . ) The 
dioenzoj'i  ueriva.  uive  insoluole  in  water,  ether,  and  petrolic  ether 
Wiiile  it  is  sofuufe  in  c^fcoiiOl,  etiijl  acetate,  anu.  cenzene. 
Analyses:  Calculated  for  C^3H^qK202>  N r 9.93/5 
Found:  (Dumas)  9.85/5  and  10.09/a  N • 

Even  When  only  one  mol  of  oenzo^l  chloride  is  added  to  1 mol  of 
the  base  the  same  derivative  is  formxSd  wnile  tne  remainder  of  tne 
Case  is  not  affected. 

Other  derivatives; Test  tube  trials  show  tnat  the  oxallate,  the 
picrate,  tiie  seinicar uaziue , and  the  aromatic  aldehyde  derivatives 
can  readily  oe  prepared.  To  prepare  tne  aliphatic  aldehyde  and 
ketone  uerivatives,  a condensing  agent  appears  to  be  necessary. 


*«rj 

j j 


. iW. 


1 


f 


I 


y 


- 69  - 


CH 


A A fV 

PKiiPAKiiriulT  OP  AGPiONE  I^OPAOP VL-HYl)RAZONE,  ^ GH-NH-N=C; 


CHg 


o 


Although  preliminary  trials  had  shown  that  a small  amount  of 
a new  compound  was  ourained  when  the  prim_ary  ayarazine  and 
acetone  were  m.ixeu,  the  yield' was  too  small  to  permit  tae  isola- 
tion and  iaentii icarion  of  rhe  new  suustance.  As  it  was  very 
urgently  desired  to  make  the  condensation  proauct  of  acetone 
and  rne  primary  ayarazine,  to  prove  , ii  possiule  , rne  strucLure 
of  tne  oxiaaLion  proauct  obtainea  from  tne  hydrocaloride  of  the 
symmeorical  hydrazine,  a long  series  of  experiments  were  carriea 
out  in  an  elforr  to  aeuermine  wnetaer  the  condensation  product 
could  ue  produceu  in  good  enouga  yiela  to  permit, au  least  , its 
isolation  and  identii ication. 

The  only  metaoa  taat  aas  seen  triea  taat  gives  good  yields 
is  tae  one  aevelopea  cy  Aeddelien  for  tne  preparation  of  aniles. 
1.5  mols  of  acetone  of  acetone  are  added  to  a solution  of  1 mol 
of  primary  isopropyl  hydrazine  in  10  volumes  of  etaer  that  has 
been  carefully  dried.  No  reaction  can  be  noticed.  A small  piece 
of  anhydrous  zinc  chloride  (less  that  ,5  g)  is  added  to  the 
mixture.  Immeaiately  tiiere  is  a violent  reaction  with  vigorous 
heating  and  euulitian  of  acetone.  To  prevent  too  large  a loss 
of  acetone  oxie  small  flash  is  cooled  unuer  tne  tap  until  the 
reaction  slows  aoim,  Tne  mixture  is  again  aeated  almost  to  tae 
uoiling  point  oi  tne  excess  acetone  and  taen  allowea  to  stand 
for  an  hour  or  two.  a.t  tae  end  of  tais  time  the  reaction  pro- 
duct is  distilled  directly  off  tne  liquid  and  clieesy  zinc  salts. 
Tlie  disLillate  is  taen  dried  over  iresaly  ariea  anhydrous  sodium 
sulphate  lor  3-4  days  before  iractionating  tne  mixture,  up  to 


70 


65°  UiG  etner  and  excess  acetone  come  over.  At  auout  65°  the 
tiiermometer  suadenij  rises  until  a temperature  oi  132°  ia 
reached.  The  rest  oi  tne  liquid  distills  over  uetween  132  and 
134  uegrees.  The  residue  left  aiter  tuis,  as  'well  as  tiie  first 
distillation  is  a deep  red  liquid  containing  zinc  salts  as  some 
of  the  residual  substances,  nhese  substances  were  not  examined 
in  detail. 

The  pure  hjdrazone  is  a colorless,  mobile  liquid  with  a 
stinging  menthol  odor  that  seems  to  be  characteriztic  of  ketone 
and  aldenyde  condensation  proaucts  v/itii  primary  isoprop^l-nydra- 
zine,  as  it  was  also  encountered  in  test  tube  experiments  with 
benzaldeiiyde  and  witii  salicylaldehyde , 

The  density  was  found  ; =,8225 

22 

The  refractive  inaex  ; T\  - 1.4360 

Analyses;  Calcuiateu  for  G = 63.15;  K = 12.28;  N r 24.56^S 

i<'ound;  G z 62.69  and  63.00)^;  H =12.47,12,5570  ; h r 24.98,24.347b 
IviOlecular  weight  ue  termination , Lowering  of  freezing  point  of 
benzene.  found  t 105,108,  104  . Theoretical  ; 114. 

The  hy drazone  is  very  easily  hydrolyzed  even  by  water.  This 
f8.ct  explains  why  it  nas  been  so  aifficult  to  obtain  alipiiatic 
hyurazones  in  tue  past.  Tlie  prouucts  of  iiydroiysis  were  identified 
in  the  sam.e  way  tlxat  tuose  obtaineu  from  the  azo  compound  were 
iaentiiied. 

Reduction  to  tne  hyarazo  compounu  v^as  readily  effected 
by  means  of  colloidal  platinum  anu  uydrogen  as  in  tne  case  of  tne 
azo  compound.  .Jie  product  obtaineu  was  iuentixied  by  the  melting 
point  of  tne  nydrocuioride  and  uj  the  odor  oi  tiie  azo  compound 


71 


ODtaineu  on  Lreaoing  Lne  arociiioriue  vjiun  powderea  copper  oxide, 
AbtempLs  oo  prepare  one  uenzoyl,  tue  puenjlmustara  oil,  and 
tile  semicar uazide  aerivatives  failed  because  , owing  lo  moisture 
periiaps,  Lne  final  proauct  obfaineu  was  always  the  corresponding 
derivative  of  the  primary  isopropyl  hyarazine.  It  is  possible 
tnat  some  of  . these  may  be  obfained  tarougir^the  use  oi’  some  de- 
hydrating agent, 

VAiilOuo  DEsEiraViIbAi  IONS  xb'Mb  IviE'friObo; - 

me  inuex  of  refraction  of  tne  uifferent  compounds  was 
aeferminea  by  means  of  an  Aube  ref ractometer  with  daylight  as 
tne  source  of  iigxiL,  liie  instrument  waa  frequenLiy  ciiecked  against 
water.  The  remperarure  was  obtainea  by  means  of  a Kormal 
tnermometer . 

The  specific  gravity  was  determined, in  each  case  ,by 
means  of  a small  moaiiieu  Sprenkel  type  picnometer.  because  of 
the  small  amounts  of  pure  material  preparea,in  most  cases, at  one 
uime,  one  capacity  of  the  picnometer  was  made  only  1,6219  cc  at 
4 degrees.  The  instrument  was  always  filled  to  the  mark  on  the 
j-ine  capillary  side  arm  at  the  temperature  at  which  ohe  sample 
and  instrument  nad  been  kept  for  some  hours.  This  temperature 
was  Known  anu  was  higher  than  that  of  the  balance  case.  When 
tne  weigiiings  were  carried  out  the  liquid  drew  av/ay  Irom  the 
tip  of  the  instrument  thus  preventing  loss  due  to  evaporation. 

To  determine  tne  strength  of  tiie  symmetrical  hydrazine,  and 
if  possible,  tnat  o±  tne  primary  nyurazine,  conductivity 
measurements  were  carried  out.  The  temperature  of  tiie  tnermo- 
stat  w^'S  kept  constant  at  25  + .01*^,  hie  ceil  nad  platinized 


( , t 


t • 


1. 


'^v 


*■'  n>''5 


c '^VWl  ’jjbw.  ii  ’'1^^ 

-ty  i.0^.,  jrti'iw 

• ' ' i'>  t - 


> i- 


72 


electrodes  faslenedjto  a verLical  uoudle  v;ire  inlet  tube, 
parallel  to  eacn  otner  and  at  a distance  ol  2.5  mm.  A stopcock 
az  zne  bottom  of  tiie  cell  permitted  the  withdrawal  of  5 cc  of 
so_^  tion  alter  eacii  dilution  wnile  tiie  added  water  was  added 
irora  an  accura.tely  calibratod  pipette.  As  the  samples  had  to  be 
kept  in  an  atmosphere  of  nitrogen,  a strong  capillary  tube 
reaciiing  into  the  bottom  of  the  cell  served  as  an  inlet  for  the 
nitrogen  wnich  served  as  a stirring  device  as  well  as  in  the 
capacity  of  an  inert  atmospnere.  This  proveu  very  satisiaciory 
as  trie  buuDles  SLirred  me  solution  txioroughly  witnout  endanger- 
ing the  adjustment  oi  tne  electroaes. 

Tiie  sourse  of  aluernaiing  current  was  a special  alterna- 
tor furnishing  1000  cycles  a second.  Tne  conductivity  water 
was  preiDarea  by  means  of  the  regular  conauciivity  water  still. 

AS  tiie  iiydrociilorivxe  is  appreciably  hydrolyzed  at  nign 
uilutions  , x^reuig's  metiiod  of  calculating  the  value  of  /\^was 
employea,  ho  claim  of  great  accuracy  is  maae  for  tne  deterraina-1 j 
lions  in  view  of  the  fact  that  it  is  very  diificult  to  prevent 
tne  base  from  oxiaizing  to  some  extent  and  the  assumption  that 
hydrolysis  does  not  enter  in  in  the  conuuctivity  determinations 
on  tne  iiydrociiloride  below  256  volumes  is  also  hardly 
justifiable.  In  view  oi  tne  limitations  places  on  tne  conductivit 
work  by  tne  nature  of  the  base, tne  fact  tnat  the  strength  of  the 
symmetrical  ease  is  very  close  to  txxat  of  hydrazine,  is  all 
that  was  hoped  i or  tne  determinations. 

The  primary  rij^drazine  pioved  to  be  extensively  nydrol- 
yzeu  even  at  16  volumes  of  water  to  1 of  oase. 


75 


TAiiXjiii  XX* 

Conauctivity , at  Variouy  Concentrations,  Of  tne  Hydrociiloriaes 


Of 

Some  nitrogen 

Voi'ojiies  of 
'jyater  per  Gram 
oaXt  • 

6 

of 

lij'aroculoride  of 

2, 2 ‘ -Hydrazo- 

propane  NpK.  (CK5)piMH 

82.1  --- 

o 

GK^wHp 

16 

102.0 

— 

— 

— 

— 

52 

116.2 

111.5 

106.5 

126.5 

115.4 

64 

150.0 

114.6 

109.7 

129.8 

116.9 

128 

140.0 

117.8 

112.6 

152.8 

119.9 

266 

160.0 

120.6 

114.0 

135.0 

122.6 

512 

175.0 

122.5 

116.2 

156.4 

123.8 

1024 

182.0 

125.0 

117.5 

157.9 

125.1 

jata,  except  for  2 ,2 ‘ -iiydrazopropane( 5^'mmetrical  diisoprop^'l 

52 

iiyuraz3)n^,  from  oreaig#' 

y 


1 • 


1 


/ 


I 

r 

t; 


./> . I 

t*,'  ' 


i 


C r 
0^  ^ 


if. 


» •» 


, V 


V • 


74 


T A3LIL  III 

|0O 

Values  of(Yir;^y7  ior  a Kumber  of  Nitrogen  Bases  at 
Various  Goncentrations . 


Base  Volumes  r 

8 16 

32 

64 

128 

256 

Average 

Hydrazine  • 

00044,0005  . 

00023 

,00021 

.00020 

.00021 

.00027 

3 ym.  Di-iso 
Propyl-hydrazine 

.00023.00022 

•00019 

.00018 

.00019 

.00020 

Aniline 

,15V  ,165 

.162 

.159 

« 156 

.152 

.158 

I-Propyl-amine 

.052  .054 

.054 

. 053 

.052 

.051 

.053 

Ammonia 

.0023  .0023 

.0025 

.0023 

.0023 

.0024 

.0023 

kethyl- amine 

.052  .052 

.051 

. 050 

.049 

.047 

, 050 

Dime  1-amine 

.074  .074 

.074 

.074 

. 0?'4 

.074 

.074 

T rime  thy 1-amine 

.0069  .0073 

. 0075 

.0076 

.0075 

.0074 

.0074 

Bata,  except  for  sjmmefricai  biisoprop^ l-xiydrazine^ f rom  Bredig^52 j 


Y5 


IV  SUMwArtY. 

1)  Tiie  reuacLion  or  (limeLliji  ketazine  to  symmetrical  diiso- 
propyl iiyurazine  nas  Deen  accompli sixea  oy  means  or  catalytic 
reduction  using  colloiaal  platinum  as  a catalyse . 

k)  rue  resulting  hydrazine  and  its  common  derivatives  have 
been  studied. 

o)  2 , 2 ’ -Azobispropane  lias  been  prepared  by  oxidaeion  of  the 
hyurociiloride  or  tne  symmetrical  h^u.razine.  The  use  or  copper 
oxiue  as  an  oxidizing  agent  to  prepare  alipnatic  azo  compounds 
constitutes  a new  metuou  oT  oxiaaeion  ol  sucn  nierogen  compounds. 

4)  Acetone-isopropyl  hyurazone  , a new  zype  o±  alipiiaeic 
compound  xias  ueen  prepa.reu  ana  studied.  The  isolaeion  or  both 
rne  azo  and  the  uydrazone  derivaoives  or  tne  symmetrical 
hydrazine  represents  an  acnievement  tnar  has  not  Heretofore 
been  accomplisned  in  the  rield  ox  purely  alipnaric  hydrazines. 

5)  Tne  mono-nitroso  derivative  of  symmetrical  diisopropyl- 
hyurazine  nab  been  prepared  and  stuv^ied. 

6)  The  rirst  sodium  salt  purely  aliphacic  nitroso  - 

hydrazine  iias  been  prepared  in  the  x orm  of  the  sodium  salt  of 
theimono-nitroso  ^erivaoive  of  the  Syrnwetrical  hydrazi-ne. 

7)  The  previously  unknown  primary  isopropyl  hydrazine  has 
boen  prepared  by  the  following  metnods; 

(a)  hy  reduction  or  a mixture  of  1 mol  of  acetone  and 
1 mol  of  nydrazine  nydrate  to  wxiicn  1 mol  of  hydrochloric  acid 
nad  been  auued. 

(b}  hy  acid  xxydrolysis  ox  acetone  isopropyl  hy drazone. 
(c)  hy  auid  xiyurolysis  or  2,2 ' -azobispropane. 


76 


TABLii  I V 

Relations  Between  tiie  Dii'ierenL  Proaucus  ..-jtuuien  in  tBe 


i X ;-.sent  InvcstijaLion. 


■/'m^  ' 

,,y.i  / 'i  . > ^.t, . 4 


- m 


1 

• it 


•,.  ^ ^;i^*  ,u  >r... ■ t %'^  ^4  t\fiui^:<§t. 

Miim  -.  ■ .JH  . . , ■'  fr;  ’■" 


't«f. 


vl‘  "iA 


'''  ’i  w'>' ’ f '*  '*  **  _ m '•»  *< 

iy'y 


f 

■d: 


,v#'A 


■ r (■ 


. tJ ' r/  4M  .Si  ,'f.  •_.. 


A *f  ' 

M:  ■''./  \h 


y." -v-  . , ■"  - '''  '■♦^  . ’/i 


!,'(l'! 


fitf 


I 


v.,j  <,<!'.^  ■'•■**  ' ' ' ' -/^ 


' ('If 


, r ,r^Vf-» " %■■  ■(  f^' . ' ".Trf 

: * * * '■*?  - ;•  ,S  y 


* f^' 


fel 


Iff-V 


"nr 

<¥f  -T 


’X" 


\ 


Oi-  **•  . . ■ ^ _ I 


vL?'il 


f*»» 


wfi:, 

.=  ■.  ■,  ■ ' 

i^'-  '-■  .If 

‘'■'®  '"rf  f t k.'*v’ 

' J'  -4t  4J!.4i«.  r.u- 


^ ' i‘X  ■ ^ . i h At:  ^ 


ir, 


*•'  ' 

(■’!  •■^1 


'-»:  ..i£l 


' rlv'' 


,ff  1 ■ 'X 


>lk^’  •*. 


* ’ 

1 1 '.' 


tA  / .'■■  / ' ■ 


L 


■f^'fi  ■ ',i^  , '’. -V. 


■ »Wg»  ^ "~* ' . ■ ---».•  ,J""^  i4Juu;i'Ujii/..Vg*^-^-!  a"---: 


76 


iJlBLIOuiiAPii  i . 

1.  Curtius,  J.  prakt  .(Jhem,  , ( 2 ) ^,531  (1888) 

2.  Raschig,  3er.^,  4587  (1907) 

3.  i‘lscher,  Ann«  ,190,71  (1878) 

4a.  i'lscher,  Ann.,  .190,  77  (1878) 

4b,  risciier,  Ann.,  199 , 308(1879) 

4c.  Riscner,  Ber.,  2i71(1880) 

5a.  Rischer,  Ann. , 199 , 325  (1879) 

5b.  RisCiier,  ibin.  , 190,102  (la78) 

6.  RiscAer  and  jrillning,  Ann.  ,253,  5 (1889) 

7a.  Rischer,  Ann. , 199, 330  (1879) 

7b.  i-i'i sober,  8er .,29,793  (1896) 

7c.  Harries  and  Haga,  8er.,_^,  58  (1898) 

8.  oLolle  and  j-jenratb,  J.prakt  .Gnem.  , ( 2 ) 70,263(  1904) 

9.  Ruscn,  DisserLaLion , Heiaeluerg,  1904, 

10.  Kisclnner,  J.  prakt  .onem. , ( 2 ) ^,113  (1901) 

lla,  Curtius,  J.  prakt  .Ciiem.  , ( 2 ) ^,44  (1889) 

llb.  Gurbius  and  Pi  lug,  J , praKt  .Gnern.  , ( 2 ) (1891) 

12a,  Curtius,  J.  prakt.  .Guem,(2)  62 , 83(  1900 ) 

12b,  Thiele,  Ann. 376, 261  (1910) 

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13b.Vvohl  and  Oesterlin,  cer .,  33, 2736 ( 19  00 ) 

14,  Curtius  and  Tnun,  J.praKL.Ghem. , ( 2)  44,161(1891) 

15,  Thiele,  Ann., £^,262  (1910) 

16,  Thiele  and  Iieusser , Ann.  ,290,30(1896) 

17, Wieland, "hie  Hydrazine,  Rerdinand  Enke , Stuttgart , 1913.p  94 


=‘-" 

♦ 


I 


V 


■■  J 


\ 


. I 


- 77  - 

18.  Iviailiie,  Compt.rena.  ,170,1265  (1920) 

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18d.  krey  ana  Horfman,  konatsh. , 22, 762(1901 ) 

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27a.  Harries,  per. ,27,2279(1894) 

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/ 


L'  u'h; 


t 


9 


I 


- 78  - 

28b,  busch,  ber.  ,^,loy(  1905) 

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29c,  Harries,  i^er .27_,22v6(  1894) 

50a,  liiiele,  Her  . , 41, 28Qb(  1908) 

50b.  Thiele,  Her., 41, 2681  (1908) 

50c.  Stolle,  Ber.,  ^,2811(1908) 

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52  ,_;amberger  and  hausser,  Ann. , 575, 519  ( 1910) 

55a.  Voswinkel,  Ber. , 55, 1945( 1910) 

54,.  pecuman,  Ber. 26, 104 7(1 89 5) 

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56.  Thiele  , Ann. ,576, 245  (1910) 

57.  Kizis,  Dissertation,  Strassburg,  (Date  not  given) 
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45a.  Fischer,  Ber . , 29 , 795( 1896) 

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- 7y  - 

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45d.  Kischner, J.prakt,Ohem. ,(2)64,125(1901) 
46a.  Headelien,  8er .42,4759( 1909 ) 

46b.  Reddelien,  6er.  ,^,2479(  1910) 

46c .Kedaelien,  ibnn.  ,588,170(1912) 


46a.  Lachowiez,iv.onaosh.  ,^,  510(  1912 ) 

46s.  keadelien,  oisseriation  ,Leipzig( 1912 ) 

47.  DimroLh  and  Zoeppritz,  ber. ,56,984(1902) 

48.  W-ieland,  J^er . ,41, 5606(  1902 ) 

49.3iiipley  anaV/erner,  J.pnem.  Soc. , 105, 1255(  1898) 


50. 

otolle. 

J.prakL.ohem. , (2)  66,552(1902) 

61. 

Storch, 

aentralbl. 1895, I ,915. 

52. 

ijredig. 

J .prakt .Ohem.  15, 508( 1891) 

55. 

Noyes, 

J.A.0.3. ,43,1779(1921) 

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Tlie  Witter  was  uorn  in  G-iilespie  Gounty,  Texas,  on 
OctoDer  18tn,  1892,  He  >^rauuateu  rrom  tue  3outiiwest  Texas  Normal 
ocxiool  in  1913, witn  History  as  tlie  major  stua^.  In  1918  iie  re- 
cieved  a B.A.  degree  i'rom  tne  University  of  Texas  v/Here  He  served 
as  student  assistant  in  1917-18,  and  as  tutor  in  1919-20. Previous 
to  and  between  nis  years  of  study  at  the  University  of  Texas,  he 
taught  for  four  years  in  various  public  schools  of  Texas. 

From  April  1918  to  September  1919,  he  served  in  the  hospital 
corps  of  the  U.S.Navy,  in  clinical  laboratory  work. 

he  vifas  a graduate  assistant  in  (jnemistry  during  1920-21 
anu  a Fellow  during  1921-22  at  tiie  University  of  Illinois, 
he  is  co-author  of  two  articles, - 

1)  "The  Conversion  of  kethyleneaminoacetonitrile  to  Iminiaceto- 
nitrile"  by  J.R.nailey  and  li.L.Locnte,  J.A.C.S.  ^,2443  (1917) 

2)  "Symmetrical  ui-Isopropyl-Hydrazine  and  Its  derivatives." 

A preliminary  article  by  the  writer  witn  J.rc.  Bailey  and  W.A.  Noyes. 
J.A.C.S.  43,2597  (1921) 


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